KR101727770B1 - Fluorourethane as an additive in a photopolymer formulation - Google Patents
Fluorourethane as an additive in a photopolymer formulation Download PDFInfo
- Publication number
- KR101727770B1 KR101727770B1 KR1020127014264A KR20127014264A KR101727770B1 KR 101727770 B1 KR101727770 B1 KR 101727770B1 KR 1020127014264 A KR1020127014264 A KR 1020127014264A KR 20127014264 A KR20127014264 A KR 20127014264A KR 101727770 B1 KR101727770 B1 KR 101727770B1
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- fluorourethane
- isocyanate
- formulation according
- photopolymer formulation
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 62
- 238000009472 formulation Methods 0.000 title claims description 27
- VUUAEBBAUMJPRE-UHFFFAOYSA-N ethyl n-fluorocarbamate Chemical compound CCOC(=O)NF VUUAEBBAUMJPRE-UHFFFAOYSA-N 0.000 title claims description 17
- 239000000654 additive Substances 0.000 title description 6
- 230000000996 additive effect Effects 0.000 title description 3
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 230000003287 optical effect Effects 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- -1 buret Chemical compound 0.000 claims description 53
- 239000005056 polyisocyanate Substances 0.000 claims description 24
- 229920001228 polyisocyanate Polymers 0.000 claims description 24
- 229910052731 fluorine Inorganic materials 0.000 claims description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 17
- 239000011737 fluorine Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical group OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 15
- 125000001153 fluoro group Chemical group F* 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004014 plasticizer Substances 0.000 claims description 4
- PJMDLNIAGSYXLA-UHFFFAOYSA-N 6-iminooxadiazine-4,5-dione Chemical compound N=C1ON=NC(=O)C1=O PJMDLNIAGSYXLA-UHFFFAOYSA-N 0.000 claims description 3
- 229920002396 Polyurea Polymers 0.000 claims description 3
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 230000005670 electromagnetic radiation Effects 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 23
- 150000001875 compounds Chemical class 0.000 description 34
- 239000012948 isocyanate Substances 0.000 description 33
- 150000002513 isocyanates Chemical class 0.000 description 30
- 239000002609 medium Substances 0.000 description 23
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 19
- 229920005862 polyol Polymers 0.000 description 18
- 150000003077 polyols Chemical class 0.000 description 18
- 150000001298 alcohols Chemical class 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
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- 238000001816 cooling Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 125000001931 aliphatic group Chemical group 0.000 description 9
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 7
- 229920005906 polyester polyol Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 6
- 150000003673 urethanes Chemical class 0.000 description 6
- KYIMHWNKQXQBDG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC Chemical compound N=C=O.N=C=O.CCCCCC KYIMHWNKQXQBDG-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000011344 liquid material Substances 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 125000006850 spacer group Chemical group 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- XFEWMFDVBLLXFE-UHFFFAOYSA-N 1-isocyanatodecane Chemical compound CCCCCCCCCCN=C=O XFEWMFDVBLLXFE-UHFFFAOYSA-N 0.000 description 4
- DLGUAUVHTOCKTB-UHFFFAOYSA-N 1-isocyanatononane Chemical compound CCCCCCCCCN=C=O DLGUAUVHTOCKTB-UHFFFAOYSA-N 0.000 description 4
- SVEMKBCPZYWEPH-UHFFFAOYSA-N 2,4,4-trimethylhexane Chemical compound CCC(C)(C)CC(C)C SVEMKBCPZYWEPH-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- PLAHQMWSZPRDKI-UHFFFAOYSA-N hexoxyboronic acid Chemical compound CCCCCCOB(O)O PLAHQMWSZPRDKI-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 150000007945 N-acyl ureas Chemical class 0.000 description 3
- 229910018286 SbF 6 Inorganic materials 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 239000004202 carbamide Substances 0.000 description 3
- 150000001718 carbodiimides Chemical class 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- ANJPRQPHZGHVQB-UHFFFAOYSA-N hexyl isocyanate Chemical compound CCCCCCN=C=O ANJPRQPHZGHVQB-UHFFFAOYSA-N 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- WPRDEDGZJLTOFJ-UHFFFAOYSA-N oxadiazin-4-imine Chemical group N=C1C=CON=N1 WPRDEDGZJLTOFJ-UHFFFAOYSA-N 0.000 description 3
- HXSACZWWBYWLIS-UHFFFAOYSA-N oxadiazine-4,5,6-trione Chemical compound O=C1ON=NC(=O)C1=O HXSACZWWBYWLIS-UHFFFAOYSA-N 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
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- 229920000515 polycarbonate Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
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- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- AHBNSOZREBSAMG-UHFFFAOYSA-N 1,5-diisocyanato-2-methylpentane Chemical compound O=C=NCC(C)CCCN=C=O AHBNSOZREBSAMG-UHFFFAOYSA-N 0.000 description 2
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 2
- RHNNQENFSNOGAM-UHFFFAOYSA-N 1,8-diisocyanato-4-(isocyanatomethyl)octane Chemical compound O=C=NCCCCC(CN=C=O)CCCN=C=O RHNNQENFSNOGAM-UHFFFAOYSA-N 0.000 description 2
- RFXBSYPBSRSQDU-UHFFFAOYSA-N 1-isocyanatoheptane Chemical compound CCCCCCCN=C=O RFXBSYPBSRSQDU-UHFFFAOYSA-N 0.000 description 2
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- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 2
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
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- 229910017008 AsF 6 Inorganic materials 0.000 description 2
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- 241000447394 Desmos Species 0.000 description 2
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
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- 239000012965 benzophenone Substances 0.000 description 2
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- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
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- VEMDBIASTFOJAF-UHFFFAOYSA-N dioxido(4,4,4-triphenylbutoxy)borane;tetrabutylazanium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.C=1C=CC=CC=1C(C=1C=CC=CC=1)(CCCOB([O-])[O-])C1=CC=CC=C1 VEMDBIASTFOJAF-UHFFFAOYSA-N 0.000 description 2
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Images
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
- C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
- C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/001—Phase modulating patterns, e.g. refractive index patterns
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/2403—Layers; Shape, structure or physical properties thereof
- G11B7/24035—Recording layers
- G11B7/24044—Recording layers for storing optical interference patterns, e.g. holograms; for storing data in three dimensions, e.g. volume storage
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
- G03H2001/026—Recording materials or recording processes
- G03H2001/0264—Organic recording material
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H2260/00—Recording materials or recording processes
- G03H2260/12—Photopolymer
Abstract
본 발명은, 매트릭스 중합체, 기록 단량체 및 광개시제를 포함하는 광중합체 제제, 광학 소자의 제조를 위한, 특히 홀로그래픽 소자 및 영상의 제조를 위한 광중합체 제제의 용도, 광중합체 제제로 제조된 홀로그래픽 매체의 조명 방법, 및 특정 플루오로우레탄에 관한 것이다.The present invention relates to a photopolymer preparation comprising a matrix polymer, a recording monomer and a photoinitiator, the use of a photopolymer preparation for the production of optical elements, in particular for the production of holographic elements and images, the use of photopolymer preparations, , And specific fluorourethanes.
Description
본 발명은, 매트릭스 중합체, 기록 단량체 및 광개시제를 포함하는 광중합체 제제, 광학 소자의 제조를 위한, 특히 홀로그래픽 소자 및 영상의 제조를 위한 광중합체 제제의 용도, 광중합체 제제를 포함하는 홀로그래픽 매체의 노출 방법, 및 특정한 플루오로우레탄에 관한 것이다.The present invention relates to a photopolymer preparation comprising a matrix polymer, a recording monomer and a photoinitiator, the use of a photopolymer preparation for the production of optical elements, in particular for the production of holographic elements and images, the use of photopolymer preparations, , And specific fluorourethanes.
WO 2008/125229 A1에는, 서두에 언급된 유형의 광중합체 제제가 기재되어 있다. 이들은 폴리우레탄계 매트릭스 중합체, 아크릴레이트계 기록 단량체 및 광개시제를 포함한다. 경화된 상태에서, 기록 단량체 및 광개시제는 폴리우레탄 매트릭스 내에 공간적 분포로 매립된다. 또한, 산업용 플라스틱을 위한 종래의 가소제인 디부틸 프탈레이트가 광중합체 제제에 첨가될 수 있다는 것이 상기 WO 문헌으로부터 공지되어 있다.WO 2008/125229 A1 describes photopolymer preparations of the type mentioned at the outset. These include a polyurethane-based matrix polymer, an acrylate-based recording monomer, and a photoinitiator. In the cured state, the recording monomer and the photoinitiator are embedded in the polyurethane matrix with a spatial distribution. It is also known from the WO literature that dibutyl phthalate, a conventional plasticizer for industrial plastics, can be added to photopolymer formulations.
하기 기재된 사용 분야에서의 광중합체 제제의 사용의 경우, 광중합체에서 홀로그래픽 노출에 의해 생성되는 굴절률 변화 Δn은 결정적인 역할을 한다. 홀로그래픽 노출 동안, 예를 들어, 간섭장 중 고강도 부위에서의 고도 굴절성인 아크릴레이트의 국소적 광중합에 의해, 신호 광 빔 및 기준 광 빔의 간섭장 (가장 간단한 경우, 2개의 평면파의 것)이 굴절률 격자 내로 맵핑된다. 광중합체의 굴절률 격자 (홀로그램)는 신호 광 빔의 모든 정보를 포함한다. 홀로그램을 기준 광 빔만으로 조명함으로써, 이어서 신호는 다시 재구성될 수 있다. 입사 기준 광의 강도와 관련하여 이와 같이 재구성된 신호의 강도는 이하에서 회절 효율, DE로 지칭한다. 2개 평면파의 중첩으로부터 형성되는 가장 간단한 경우의 홀로그램에서, DE는 재구성에서 회절되는 광의 강도와 입사 기준 광 및 회절 광의 강도의 합계의 비율로부터 얻어진다. DE가 높을수록, 고정된 휘도로 신호를 가시적이 되도록 하는 데 필요한 기준 광의 필수적 양의 측면에서 홀로그램이 보다 효율적이다. 고도 굴절성 아크릴레이트는, 최소 굴절률을 갖는 영역과 최고 굴절률을 갖는 영역 사이에 높은 진폭을 가지며, 그에 따라 광중합체 제제에서 높은 DE 및 높은 Δn을 갖는 홀로그램을 허용하는 굴절률 격자를 생성시킬 수 있다. DE는 Δn과 광중합체 층 두께 d의 곱에 따라 달라진다는 것에 유의해야 한다. 곱이 클수록 (반사 홀로그램의 경우) 가능한 DE는 더 크게 된다. 홀로그램이 예를 들어 단색광 조명시 가시적인 (재구성되는) 각도 범위의 폭은 층 두께 d에만 의존한다. 예를 들어 백색광을 사용한 홀로그램의 조명시, 홀로그램의 재구성에 기여할 수 있는 스펙트럼 범위의 폭은 마찬가지로 층 두께 d에만 의존한다. 이 경우 d가 더 작을수록, 각각의 허용 폭은 더 커진다. 따라서, 밝고 용이하게 볼 수 있는 홀로그램을 제조하고자 한다면, 높은 Δn·d 및 작은 두께 d가 바람직하고, 따라서 특히 DE가 가능한 한 클 것이다. 이는 Δn이 높을수록, d의 적합화에 의해 또한 DE의 손실 없이 밝은 홀로그램을 제조하기 위한 허용 범위가 더 크다는 것을 의미한다. 따라서, 광중합체 제제의 최적화에서 Δn의 최적화는 대단히 중요하다 (문헌 [P. Hariharan, Optical Holography, 2nd Edition, Cambridge University Press, 1996]).In the case of the use of photopolymer formulations in the field of application described below, the refractive index change? N produced by the holographic exposure in the photopolymer plays a crucial role. During holographic exposure, for example, by local photopolymerization of highly refractory acrylates at high intensity sites in the interference field, the interference field of the signal light beam and the reference light beam (in the simplest case of two plane waves) Are mapped into the refractive index grating. The refractive index grating (hologram) of the photopolymer contains all the information of the signal light beam. By illuminating the hologram with only the reference light beam, the signal can then be reconstructed again. The intensity of the reconstructed signal with respect to the intensity of the incident reference light is referred to below as the diffraction efficiency, DE. In the simplest case hologram formed from superposition of two plane waves, DE is obtained from the ratio of the intensity of the light diffracted in the reconstruction and the sum of the intensity of the incident reference light and the intensity of the diffracted light. The higher the DE, the more efficient the hologram is in terms of the required amount of reference light required to make the signal visible at a fixed brightness. The highly refractive acrylate can have a high amplitude between the region having the smallest refractive index and the region having the highest refractive index, thereby producing a refractive index grating that allows holograms having high DE and high? N in the photopolymer formulation. It should be noted that DE depends on the product of? N and the photopolymer layer thickness d. The larger the product (in the case of reflective holograms), the larger the possible DE. The width of the angular range in which the hologram is visible (reconstructed), for example in monochromatic illumination, depends only on the layer thickness d. For example, in the illumination of a hologram using white light, the width of the spectral range that can contribute to the reconstruction of the hologram also depends only on the layer thickness d. In this case, the smaller the value of d, the larger the permissible width of each. Therefore, if it is intended to produce a hologram that is bright and easy to see, a high? N d and a small thickness d are preferred, and therefore DE will be as large as possible. This means that the higher the [Delta] n, the greater the allowable range for fabricating a bright hologram without loss of DE by adaptation of d. Thus, optimization of [Delta] n in the optimization of photopolymer formulation is of great importance (P. Hariharan, Optical Holography, 2nd Edition, Cambridge University Press, 1996).
본 발명의 목적은, 공지된 제제와 비교하여 더 큰 휘도를 갖는 홀로그램의 제조를 허용하는 광중합체 제제를 제공하는 것이었다.It was an object of the present invention to provide a photopolymer formulation which permits the production of holograms with greater brightness compared to known formulations.
상기 목적은 가소제로서 플루오로우레탄을 포함한다는 사실에 의해 본 발명에 따른 광중합체 제제의 경우에 달성된다. 따라서, 공지된 광중합체 제제로의 플루오로우레탄의 첨가는 그로부터 제조된 홀로그램에서의 높은 Δn 값으로 이어진다는 것을 발견하였다. 그 결과, 이는 본 발명에 따른 제제로부터 제조된 홀로그램이 공지된 홀로그램에 비해 더 높은 휘도를 갖는다는 것을 의미한다.This object is achieved in the case of the photopolymer preparations according to the invention by the fact that they contain fluorourethanes as plasticizers. Thus, it has been found that the addition of fluorourethanes to known photopolymer formulations results in high Δn values in the holograms produced therefrom. As a result, this means that the hologram produced from the preparation according to the invention has a higher luminance than the known hologram.
플루오로우레탄은 바람직하게는 하기 화학식 I의 구조 요소를 갖고, 1개 이상의 플루오린 원자에 의해 치환된 화합물이다.Fluorourethane is preferably a compound having a structural element of the formula (I) and substituted by at least one fluorine atom.
<화학식 I>(I)
플루오로우레탄이 하기 화학식 II를 갖는 경우가 보다 바람직하다.It is more preferable that the fluorourethane has the following formula (II).
<화학식 II>≪
상기 식에서, n은 ≥ 1이며, n은 ≤ 8이고, R1, R2, R3은 수소이고/거나, 서로 독립적으로 비치환되거나 또는 임의로 또한 헤테로원자에 의해 치환된 선형, 분지형, 시클릭 또는 헤테로시클릭 유기 라디칼이며, 라디칼 R1, R2, R3 중 적어도 1개는 1개 이상의 플루오린 원자에 의해 치환된다. R1이 1개 이상의 플루오린 원자를 갖는 유기 라디칼인 것이 본원에서 특히 바람직하다.Wherein n is ≥ 1, n is ≤ 8, R 1 , R 2 , and R 3 are hydrogen and / or are independently selected from linear, branched, or cyclic Or a heterocyclic organic radical, and at least one of the radicals R 1 , R 2 , R 3 is substituted by one or more fluorine atoms. It is particularly preferred herein that R < 1 > is an organic radical having at least one fluorine atom.
추가 실시양태에 따르면, R1은 1 내지 20개의 CF2 기 및/또는 1개 이상의 CF3 기, 특히 바람직하게는 1 내지 15개의 CF2 기 및/또는 1개 이상의 CF3 기, 특히 바람직하게는 1 내지 10개의 CF2 기 및/또는 1개 이상의 CF3 기, 매우 특히 바람직하게는 1 내지 8개의 CF2 기 및/또는 1개 이상의 CF3 기를 포함할 수 있고/거나, R2는 C1-C20 알킬 라디칼, 바람직하게는 C1-C15 알킬 라디칼, 특히 바람직하게는 C1-C10 알킬 라디칼, 또는 수소를 포함할 수 있고/거나, R3은 C1-C20 알킬 라디칼, 바람직하게는 C1-C15 알킬 라디칼, 특히 바람직하게는 C1-C10 알킬 라디칼, 또는 수소를 포함할 수 있다.Added according to the embodiments, R 1 is 1 to 20 CF 2 groups and / or one or more CF 3 groups, and particularly preferably 1 to 15 CF 2 group and / or at least one CF 3 group, an especially preferred May contain from 1 to 10 CF 2 groups and / or at least one CF 3 group, very particularly preferably from 1 to 8 CF 2 groups and / or at least one CF 3 group, and / or R 2 is selected from the group consisting of C1 -C20 alkyl radical, preferably a C1-C15 alkyl radical, and particularly preferably C1-C10 alkyl radical, or may contain hydrogen and / or, R 3 is C1-C20 alkyl radical, preferably a C1-C15 alkyl Radical, particularly preferably a Cl-ClO alkyl radical, or hydrogen.
플루오로우레탄이 우레트디온, 이소시아누레이트, 뷰렛, 알로파네이트, 폴리우레아, 옥사디아자디온 및/또는 이미노옥사디아진디온 구조 요소 및/또는 이러한 구조 요소의 혼합물을 갖는 경우가 특히 바람직하다.Particular preference is given to fluorourethanes having uretdione, isocyanurate, buret, allophanate, polyurea, oxadiazadione and / or iminooxyadinedione structural elements and / or mixtures of such structural elements Do.
특히 플루오로우레탄은 ≤ 1.4600, 바람직하게는 ≤ 1.4500, 특히 바람직하게는 ≤ 1.4400, 특별히 바람직하게는 ≤ 1.4300의 굴절률 을 가질 수 있다.Particularly fluorourethane has a refractive index of ≤ 1.4600, preferably ≤ 1.4500, particularly preferably ≤ 1.4400, particularly preferably ≤ 1.4300 Lt; / RTI >
플루오로우레탄은 10 내지 80 중량%의 플루오린, 바람직하게는 12.5 내지 75 중량%의 플루오린, 특히 바람직하게는 15 내지 70 중량%의 플루오린, 특별히 바람직하게는 17.5 내지 65 중량%의 플루오린의 플루오린 함량을 가질 수 있다.Fluorourethane is used in an amount of 10 to 80% by weight of fluorine, preferably 12.5 to 75% by weight of fluorine, particularly preferably 15 to 70% by weight of fluorine, particularly preferably 17.5 to 65% by weight of fluorine Lt; RTI ID = 0.0 > fluorine < / RTI >
화학식 III의 플루오로우레탄은, 화학식 R[NCO]n의 이소시아네이트를 플루오린화 알콜과 서로에 대해 화학량론적 비로 반응시킴으로써 우레탄 형성 하에 얻을 수 있다.Fluorourethanes of formula (III) can be obtained under urethane formation by reacting an isocyanate of the formula R [NCO] n with a fluorinated alcohol in a stoichiometric ratio with respect to each other.
바람직한 화학식 R[NCO]n의 이소시아네이트는, 메틸 이소시아네이트, 에틸 이소시아네이트, 이성질체 프로필 이소시아네이트, 이성질체 부틸 이소시아네이트, 이성질체 펜틸 이소시아네이트, 이성질체 헥실 이소시아네이트, 이성질체 헵틸 이소시아네이트, 이성질체 옥틸 이소시아네이트, 이성질체 노닐 이소시아네이트, 이성질체 데실 이소시아네이트, 스테아릴 이소시아네이트, 시클로프로필 이소시아네이트, 시클로부틸 이소시아네이트, 시클로펜틸 이소시아네이트, 시클로헥실 이소시아네이트, 시클로헵틸 이소시아네이트, 2-메틸펜탄 1,5-디이소시아네이트 (MPDI), 도데카메틸렌 디이소시아네이트, 1,8-디이소시아네이토-4-(이소시아네이토메틸)옥탄 (TIN), 6-디이소시아네이토헥산 (HDI, 데스모두르(Desmodur) H), 1-이소시아네이토-3,3,5-트리메틸-5-이소시아네이토메틸시클로헥산 (IPDI, 데스모두르 I), 2,4,4-트리메틸헥산 1,6-디이소시아네이트 (TMDI), 디시클로헥실메탄 디이소시아네이트 (데스모두르 W), 헥사히드로톨릴렌 디이소시아네이트 (H6TDI), 비스(4-이소시아네이토시클로헥실)메탄 (H12-MDI), 1,3-비스(이소시아네이토메틸)시클로헥산, 데스모두르 LD, 데스모두르 N 100, 데스모두르 N3200, 데스모두르 N3300, 데스모두르 N3350, 데스모두르 N3368, 데스모두르 N3375, 데스모두르 N3390, 데스모두르 N3400, 데스모두르 N3600, 데스모두르 N3790, 데스모두르 N3800, 데스모두르 N3900, 데스모두르 N50, 데스모두르 N75, 데스모두르 NZ1, 데스모두르 PL340, 데스모두르 PL350, 데스모두르 PM76, 데스모두르 BL3175, 데스모두르 BL3272, 데스모두르 BL3370, 데스모두르 BL3475, 데스모두르 BL4265, 데스모두르 BL5375, 데스모두르 BLXP2677, 데스모두르 DA-L, 데스모두르 DN, 데스모두르 E 305, 데스모두르 E3265, 데스모두르 E3370, 베이마이크론(Baymicron) OXA, 데스모두르 VP LS 2078/2, 데스모두르 VP LS 2114/1, 데스모두르 VP LS 2257, 데스모두르 VP LS 2352/1, 데스모두르 VP LS 2371, 데스모두르 VP LS 2376/1, 데스모두르 XP 2406, 데스모두르 XP 2489, 데스모두르 XP 2565, 데스모두르 XP 2580, 데스모두르 XP 2599, 데스모두르 XP 2617, 데스모두르 XP 2626, 데스모두르 XP 2675, 데스모두르 XP 2679, 데스모두르 XP 2714, 데스모두르 XP 2730, 데스모두르 XP 2731, 데스모두르 XP 2742, 데스모두르 XP 2748, 데스모두르 Z 4470 또는 이들의 혼합물이다.Preferred isocyanates of the formula R [NCO] n are selected from the group consisting of methyl isocyanate, ethyl isocyanate, isomeric isocyanate, isomeric butyl isocyanate, isomeric pentyl isocyanate, isomeric hexyl isocyanate, isomeric heptyl isocyanate, isomeric octyl isocyanate, isomeric nonyl isocyanate, isomeric decyl isocyanate, Cyclohexyl isocyanate, cycloheptyl isocyanate, 2-
특히 바람직한 화학식 R[NCO]n의 이소시아네이트는, 이성질체 프로필 이소시아네이트, 이성질체 부틸 이소시아네이트, 이성질체 펜틸 이소시아네이트, 이성질체 헥실 이소시아네이트, 이성질체 헵틸 이소시아네이트, 이성질체 옥틸 이소시아네이트, 이성질체 노닐 이소시아네이트, 이성질체 데실 이소시아네이트, 스테아릴 이소시아네이트, 1,8-디이소시아네이토-4-(이소시아네이토메틸)옥탄 (TIN), 6-디이소시아네이토헥산 (HDI, 데스모두르 H), 1-이소시아네이토-3,3,5-트리메틸-5-이소시아네이토메틸시클로헥산 (IPDI, 데스모두르 I), 2,4,4-트리메틸헥산 1,6-디이소시아네이트 (TMDI), 디시클로헥실메탄 디이소시아네이트 (데스모두르 W), 헥사히드로톨릴렌 디이소시아네이트 (H6TDI), 1,3-비스(이소시아네이토메틸)시클로헥산, 데스모두르 LD, 데스모두르 N3400, 데스모두르 N3600, 베이마이크론 OXA 또는 이들의 혼합물이다.Particularly preferred isocyanates of the formula R [NCO] n are selected from the group consisting of isomeric isocyanates, isomeric butylisocyanates, isomeric pentylisocyanates, isomeric hexylisocyanates, isomeric heptylisocyanates, isomeric octylisocyanates, isomeric nonylisocyanates, isomeric decylisocyanates, stearylisocyanates, (Isocyanatomethyl) octane (TIN), 6-diisocyanatohexane (HDI, des all leh), 1-isocyanato-3,3,5-
매우 특히 바람직한 화학식 R[NCO]n의 이소시아네이트는, 이소프로필 이소시아네이트, n-부틸 이소시아네이트, n-헥실 이소시아네이트, n-옥틸 이소시아네이트, n-데실 이소시아네이트, 시클로헥실 이소시아네이트, 스테아릴 이소시아네이트, 1,8-디이소시아네이토-4-(이소시아네이토메틸)옥탄 (TIN), 6-디이소시아네이토헥산 (HDI, 데스모두르 H), 1-이소시아네이토-3,3,5-트리메틸-5-이소시아네이토메틸시클로헥산 (IPDI, 데스모두르 I), 2,4,4-트리메틸헥산 1,6-디이소시아네이트 (TMDI), 디시클로헥실메탄 디이소시아네이트 (데스모두르 W), 헥사히드로톨릴렌 디이소시아네이트 (H6TDI), 1,3-비스(이소시아네이토메틸)시클로헥산, 데스모두르 LD, 데스모두르 N3400, 데스모두르 N3600, 데스모두르 N3900, 베이마이크론 OXA 또는 이들의 혼합물이다.Very particularly preferred isocyanates of the formula R [NCO] n are selected from the group consisting of isopropyl isocyanate, n-butyl isocyanate, n-hexyl isocyanate, n-octyl isocyanate, n-decyl isocyanate, cyclohexyl isocyanate, stearyl isocyanate, (Isocyanatoethyl) octane (TIN), 6-diisocyanatohexane (HDI, des all leh), 1-isocyanato-3,3,5-trimethyl- (IPDI, Death All I), 2,4,4-
플루오린화 알콜의 가능한 선택은 광범위하고, 30% 내지 82%의 플루오린의 플루오린 함량을 갖는, 특히 바람직하게는 40% 내지 80%의 플루오린의 플루오린 함량을 갖는, 특별히 바람직하게는 49% 내지 75%의 플루오린의 플루오린 함량을 갖는 1급 또는 2급, 일-, 이- 또는 삼관능성 알콜을 사용하는 것이 바람직하다.The possible choice of the fluorinated alcohol is wide and is particularly preferably 49% with a fluorine content of fluorine of 30% to 82%, particularly preferably with a fluorine content of 40% to 80% Di-, tri-, or trifunctional alcohols having a fluorine content of about 75% to about 75% fluorine.
플루오로우레탄의 제조를 위한 상기 각 경우에서 언급된 유형의 알콜과 이소시아네이트의 반응은 우레탄화이다. 반응은 이소시아네이트 부가 반응을 촉진시키기 위한 공지된 촉매, 예컨대 3급 아민, 주석, 아연, 철 또는 비스무트 화합물, 특히 트리에틸아민, 1,4-디아자비시클로[2.2.2]옥탄, 비스무트 옥토에이트, 아연 옥토에이트 또는 디부틸주석 디라우레이트 (이는 초기에 도입되거나 이후에 계량첨가될 수 있음)의 도움으로 수행될 수 있다.The reaction of an isocyanate with an alcohol of the type mentioned in each of the above cases for the production of fluorourethanes is urethanization. The reaction may be carried out in the presence of a known catalyst for promoting isocyanate addition reaction, such as tertiary amines, tin, zinc, iron or bismuth compounds, especially triethylamine, 1,4-diazabicyclo [2.2.2] octane, bismuthoctoate, Zinc octoate or dibutyltin dilaurate, which may be introduced initially or may be metered in subsequently.
플루오로우레탄은 0.5 중량% 미만, 바람직하게는 0.2 중량% 미만, 특히 바람직하게는 0.1 중량% 미만의 이소시아네이트 기 (M = 42 g/mol) 또는 유리 이소시아네이트 라디칼 단량체의 함량을 가질 수 있다.Fluorourethanes may have an isocyanate group (M = 42 g / mol) or a free isocyanate radical monomer content of less than 0.5% by weight, preferably less than 0.2% by weight, particularly preferably less than 0.1% by weight.
또한, 플루오로우레탄은 1 중량% 미만, 바람직하게는 0.5 중량%, 특별히 바람직하게는 0.2 중량% 미만의 미반응된 히드록시-관능성 화합물의 함량을 가질 수 있다.The fluorourethanes may also have an unreacted hydroxy-functional compound content of less than 1% by weight, preferably 0.5% by weight, particularly preferably less than 0.2% by weight.
플루오로우레탄은 10 내지 80 중량%의 플루오린, 바람직하게는 12.5 내지 75 중량%의 플루오린, 특히 바람직하게는 15 내지 70 중량%의 플루오린, 특별히 바람직하게는 17.5 내지 65 중량%의 플루오린의 플루오린 함량을 가질 수 있다.Fluorourethane is used in an amount of 10 to 80% by weight of fluorine, preferably 12.5 to 75% by weight of fluorine, particularly preferably 15 to 70% by weight of fluorine, particularly preferably 17.5 to 65% by weight of fluorine Lt; RTI ID = 0.0 > fluorine < / RTI >
플루오로우레탄은 ≤ 1.4600, 바람직하게는 ≤ 1.4500, 특히 바람직하게는 ≤ 1.4400, 특별히 바람직하게는 ≤ 1.4300의 굴절률 을 갖는다.Fluorourethanes have a refractive index of ≤ 1.4600, preferably ≤ 1.4500, particularly preferably ≤ 1.4400, particularly preferably ≤ 1.4300 Respectively.
플루오로우레탄의 제조에서는, 이소시아네이트 및 알콜을 비반응성 용매, 예를 들어 방향족 또는 지방족 탄화수소, 또는 방향족 또는 지방족 할로겐화 탄화수소 또는 코팅 용매, 예컨대 에틸 아세테이트 또는 부틸 아세테이트 또는 아세톤 또는 부타논 또는 에테르, 예컨대 테트라히드로푸란 또는 tert-부틸 메틸 에테르 또는 이중극성 비양성자성 용매, 예컨대 디메틸 술폭시드 또는 N-메틸피롤리돈 또는 N-에틸피롤리돈에 각각 용해시킬 수 있고, 이는 당업자에게 통상적인 방식으로 초기에 도입하거나 계량첨가할 수 있다.In the preparation of fluorourethanes, the isocyanates and alcohols are reacted in a non-reactive solvent such as an aromatic or aliphatic hydrocarbon, or an aromatic or aliphatic halogenated hydrocarbon or a coating solvent such as ethyl acetate or butyl acetate or acetone or butanone or an ether such as tetrahydrofuran Furan or tert-butyl methyl ether or a dipolar aprotic solvent such as dimethylsulfoxide or N-methylpyrrolidone or N-ethylpyrrolidone, respectively, which may be introduced initially in a manner customary to those skilled in the art Or metered addition.
반응 종결 후, 비반응성 용매를 대기압 하에 또는 감압 하에 혼합물로부터 제거하고, 고체 함량을 측정함으로써 종결점을 결정할 수 있다. 고체 함량은 플루오로우레탄을 기준으로, 전형적으로 99.999 내지 95.0 중량%, 바람직하게는 99.998 내지 98.0 중량%의 범위이다.After termination of the reaction, the end point can be determined by removing the non-reactive solvent from the mixture under atmospheric or reduced pressure and measuring the solids content. The solids content is typically in the range of 99.999 to 95.0% by weight, preferably 99.998 to 98.0% by weight, based on the fluorourethane.
매트릭스 중합체는 특히 폴리우레탄일 수 있다. 바람직하게는, 폴리우레탄은 이소시아네이트 성분 a)를 이소시아네이트-반응성 성분 b)와 반응시킴으로써 얻을 수 있다.The matrix polymer may in particular be a polyurethane. Preferably, the polyurethane can be obtained by reacting isocyanate component a) with isocyanate-reactive component b).
이소시아네이트 성분 a)는 바람직하게는 폴리이소시아네이트를 포함한다. 사용가능한 폴리이소시아네이트는, 분자 당 평균 2개 이상의 NCO 관능기를 갖는, 그 자체로 당업자에게 익히 공지되어 있는 모든 화합물 또는 그의 혼합물일 수 있다. 이들은 방향족, 아르지방족, 지방족 또는 시클로지방족 기재의 것들일 수 있다. 최소의 양으로, 불포화 기를 함유하는 모노이소시아네이트 및/또는 폴리이소시아네이트를 동시에 사용하는 것 또한 가능하다.The isocyanate component a) preferably comprises a polyisocyanate. The polyisocyanates which can be used are all compounds which are known per se to the person skilled in the art, or mixtures thereof, having on average more than 2 NCO functional groups per molecule. These may be aromatic, araliphatic, aliphatic or cycloaliphatic based. It is also possible to use mono isocyanate and / or polyisocyanate containing an unsaturated group in a minimum amount at the same time.
예를 들어, 부틸렌 디이소시아네이트, 헥사메틸렌 디이소시아네이트 (HDI), 이소포론 디이소시아네이트 (IPDI), 1,8-디이소시아네이토-4-(이소시아네이토메틸)옥탄, 2,2,4- 및/또는 2,4,4-트리메틸헥사메틸렌 디이소시아네이트, 이성질체 비스(4,4'-이소시아네이토시클로헥실)메탄 및 임의의 요망되는 이성질체 함량을 갖는 그의 혼합물, 이소시아네이토메틸-1,8-옥탄 디이소시아네이트, 1,4-시클로헥실렌 디이소시아네이트, 이성질체 시클로헥산디메틸렌 디이소시아네이트, 1,4-페닐렌 디이소시아네이트, 2,4- 및/또는 2,6-톨루엔 디이소시아네이트, 1,5-나프틸렌 디이소시아네이트, 2,4'- 또는 4,4'-디페닐메탄 디이소시아네이트 및/또는 트리페닐메탄 4,4',4"-트리이소시아네이트가 적합하다.For example, butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4- (isocyanatomethyl) - and / or 2,4,4-trimethylhexamethylene diisocyanate, isomeric bis (4,4'-isocyanatocyclohexyl) methane and mixtures thereof with any desired isomeric content, isocyanatomethyl- Cyclohexylene diisocyanate, isomeric cyclohexane dimethylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,5'-naphthylene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate and / or triphenylmethane 4,4 ', 4 "-triisocyanate are suitable.
우레탄, 우레아, 카르보디이미드, 아실우레아, 이소시아누레이트, 알로파네이트, 뷰렛, 옥사디아진트리온, 우레트디온 및/또는 이미노옥사디아진디온 구조를 갖는 단량체 디- 또는 트리이소시아네이트의 유도체의 사용도 또한 가능하다.Of a monomeric di- or triisocyanate having an urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, buret, oxadiazinetrione, uretdione and / or iminooxadiazine structure Use is also possible.
지방족 및/또는 시클로지방족 디- 또는 트리이소시아네이트를 기재로 하는 폴리이소시아네이트의 사용이 바람직하다.The use of polyisocyanates based on aliphatic and / or cycloaliphatic di- or triisocyanates is preferred.
특히 바람직하게는, 성분 a)의 폴리이소시아네이트는 이량체화 또는 올리고머화된 지방족 및/또는 시클로지방족 디- 또는 트리이소시아네이트이다.Particularly preferably, the polyisocyanate of component a) is a dimerized or oligomerized aliphatic and / or cycloaliphatic di- or triisocyanate.
HDI, 1,8-디이소시아네이토-4-(이소시아네이토메틸)옥탄 또는 이들의 혼합물을 기재로 하는 이소시아누레이트, 우레트디온 및/또는 이미노옥사디아진디온이 매우 특히 바람직하다.Very particular preference is given to isocyanurate, uretdione and / or iminooxadiazinedione based on HDI, 1,8-diisocyanato-4- (isocyanatomethyl) octane or mixtures thereof .
우레탄, 알로파네이트, 뷰렛 및/또는 아미드 기를 갖는 NCO-관능성 예비중합체가 성분 a)로서 사용될 수도 있다. 성분 a)의 예비중합체는 임의로 촉매 및 용매를 사용하여, 단량체, 올리고머 또는 폴리이소시아네이트 a1)을 적합한 화학량론으로 이소시아네이트-반응성 화합물 a2)와 반응시킴으로써, 당업자에게 그 자체로 익히 공지된 방식으로 얻어진다.NCO-functional prepolymers having urethane, allophanate, burette and / or amide groups may also be used as component a). The prepolymer of component a) is obtained in a manner known per se to the person skilled in the art, optionally by reacting the monomers, oligomers or polyisocyanates a1) with isocyanate-reactive compounds a2), with suitable stoichiometry, using catalysts and solvents .
적합한 폴리이소시아네이트 a1)은 당업자에게 그 자체로 공지되어 있는 모든 지방족, 시클로지방족, 방향족 또는 아르지방족 디- 및 트리이소시아네이트이며, 이들이 포스겐화에 의해, 또는 포스겐-무함유 공정에 의해 수득되었는지의 여부는 중요하지 않다. 또한, 당업자에게 그 자체로 익히 공지되어 있는, 우레탄, 우레아, 카르보디이미드, 아실우레아, 이소시아누레이트, 알로파네이트, 뷰렛, 옥사디아진트리온, 우레트디온 또는 이미노옥사디아진디온 구조를 갖는 단량체 디- 및/또는 트리이소시아네이트의 고분자량 2차 생성물을 각 경우에 개별적으로 또는 임의의 요망되는 서로와의 혼합물로서 사용할 수도 있다.Suitable polyisocyanates al) are all aliphatic, cycloaliphatic, aromatic or araliphatic di- and triisocyanates known per se to the person skilled in the art and whether they are obtained by phosgenation or by a phosgene-free process It is not important. It is also possible to use urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, buret, oxadiazinetrione, uretdione or iminooxadiazinedione structures well known per se to those skilled in the art The high molecular weight secondary products of the monomeric di- and / or triisocyanates which may be used in each case individually or as a mixture with any desired one.
성분 a1)으로서 사용될 수 있는 적합한 단량체 디- 또는 트리이소시아네이트의 예는, 부틸렌 디이소시아네이트, 헥사메틸렌 디이소시아네이트 (HDI), 이소포론 디이소시아네이트 (IPDI), 트리메틸헥사메틸렌 디이소시아네이트 (TMDI), 1,8-디이소시아네이토-4-(이소시아네이토메틸)옥탄, 이소시아네이토메틸-1,8-옥탄 디이소시아네이트 (TIN), 2,4- 및/또는 2,6-톨루엔 디이소시아네이트이다.Examples of suitable monomeric di- or triisocyanates that can be used as component a1) include butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), 1, Diisocyanato-4- (isocyanatomethyl) octane, isocyanatoethyl-1,8-octane diisocyanate (TIN), 2,4- and / or 2,6- toluene diisocyanate .
바람직하게는 OH-관능성 화합물이 예비중합체의 합성을 위한 이소시아네이트-반응성 화합물 a2)로서 사용된다. 이는 성분 b)에 대해 하기에 기재하는 바와 같은 OH-관능성 화합물과 유사하다.Preferably the OH-functional compound is used as the isocyanate-reactive compound a2) for the synthesis of prepolymers. This is analogous to the OH-functional compounds as described below for component b).
예비중합체 제조를 위한 아민의 사용 또한 가능하다. 예를 들어 에틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라민, 프로필렌디아민, 디아미노시클로헥산, 디아미노벤젠, 디아미노비스페닐, 이관능성 폴리아민, 예컨대 제파민(Jeffamine)®, 10,000 g/mol 이하의 수 평균 몰 질량을 갖는 아민-말단 중합체 또는 이들의 임의의 요망되는 서로와의 혼합물이 적합하다.The use of amines for preparing prepolymers is also possible. For example, ethylene diamine, diethylene triamine, triethylene tetramine, propylene diamine, diaminocyclohexane, diaminobenzene, Dia US nobiseu phenyl, di-functional polyamines, such as Jeffamine (Jeffamine) ®, 10,000 g / mol or less Of the number average molecular mass or mixtures thereof with any desired one are suitable.
뷰렛 기를 함유하는 예비중합체의 제조를 위해, 이소시아네이트를 과량으로 아민과 반응시키고, 여기서 과정 중에 뷰렛 기가 형성된다. 언급된 디-, 트리- 및 폴리이소시아네이트와의 반응을 위해 이 경우에 적합한 아민은 상기 언급된 유형의 모든 올리고머 또는 중합체 1급 또는 2급 이관능성 아민이다.For the preparation of prepolymers containing biuret groups, the isocyanates are reacted with an excess of an amine, wherein a biuret group is formed during the process. Suitable amines in this case for the reaction with the mentioned di-, tri- and polyisocyanates are all oligomeric or polymeric primary or secondary difunctional amines of the type mentioned above.
바람직한 예비중합체는 수 평균 몰 질량이 200 내지 10,000 g/mol인 올리고머 또는 중합체 이소시아네이트-반응성 화합물 및 지방족 이소시아네이트-관능성 화합물로부터 얻은 우레탄, 알로파네이트 또는 뷰렛이며; 수 평균 몰 질량이 500 내지 8500 g/mol인 올리고머 또는 중합체 폴리올 또는 폴리아민 및 지방족 이소시아네이트-관능성 화합물로부터 얻은 우레탄, 알로파네이트 또는 뷰렛이 특히 바람직하고, 수 평균 몰 질량이 1000 내지 8200 g/mol인 이관능성 폴리에테르 폴리올 및 HDI 또는 TMDI로부터 얻은 알로파네이트가 매우 특히 바람직하다.Preferred prepolymers are urethanes, allophanates or burettes obtained from oligomeric or polymeric isocyanate-reactive compounds having a number average molar mass of from 200 to 10,000 g / mol and aliphatic isocyanate-functional compounds; Particular preference is given to oligomers or polymeric polyols or polyamines having a number average molar mass of from 500 to 8500 g / mol and urethanes, allophanates or burettes obtained from aliphatic isocyanate-functional compounds and having a number average molar mass of from 1000 to 8200 g / mol Phosphorus difunctional polyether polyols and allophanates from HDI or TMDI are very particularly preferred.
바람직하게는, 상기 기재된 예비중합체는 1 중량% 미만, 특히 바람직하게는 0.5 중량% 미만, 매우 특히 바람직하게는 0.2 중량% 미만의 유리 단량체 이소시아네이트의 나머지 함량을 갖는다.Preferably, the prepolymer described above has a residual content of free monomeric isocyanate of less than 1% by weight, particularly preferably less than 0.5% by weight, very particularly preferably less than 0.2% by weight.
물론, 이소시아네이트 성분은 기재된 예비중합체 이외의 추가의 이소시아네이트 성분을 비례적으로 함유할 수 있다. 이를 위하여 방향족, 아르지방족, 지방족 및 시클로지방족 디-, 트리- 또는 폴리이소시아네이트가 적합하다. 상기 디-, 트리- 또는 폴리이소시아네이트의 혼합물을 사용하는 것 또한 가능하다. 적합한 디-, 트리- 또는 폴리이소시아네이트의 예는, 부틸렌 디이소시아네이트, 헥사메틸렌 디이소시아네이트 (HDI), 이소포론 디이소시아네이트 (IPDI), 1,8-디이소시아네이토-4-(이소시아네이토메틸)옥탄, 2,2,4- 및/또는 2,4,4-트리메틸헥사메틸렌 디이소시아네이트 (TMDI), 이성질체 비스(4,4'-이소시아네이토시클로헥실)메탄 및 임의의 요망되는 이성질체 함량을 갖는 이들의 혼합물, 이소시아네이토메틸-1,8-옥탄 디이소시아네이트, 1,4-시클로헥실렌 디이소시아네이트, 이성질체 시클로헥산디메틸렌 디이소시아네이트, 1,4-페닐렌 디이소시아네이트, 2,4- 및/또는 2,6-톨릴렌 디이소시아네이트, 1,5-나프틸렌 디이소시아네이트, 2,4'- 또는 4,4'-디페닐메탄 디이소시아네이트, 트리페닐메탄 4,4',4"-트리이소시아네이트 또는 우레탄, 우레아, 카르보디이미드, 아실우레아, 이소시아누레이트, 알로파네이트, 뷰렛, 옥사디아진트리온, 우레트디온 또는 이미노옥사디아진디온 구조를 갖는 이들의 유도체 및 이들의 혼합물이다. 적합한 방법에 의해 과량의 디이소시아네이트로부터 유리된 올리고머화 및/또는 유도체화된 디이소시아네이트를 기재로 하는 폴리이소시아네이트, 특히 헥사메틸렌 디이소시아네이트의 그것들이 바람직하다. HDI의 올리고머 이소시아누레이트, 우레트디온 및 이미노옥사디아진디온 및 이들의 혼합물이 특히 바람직하다.Of course, the isocyanate component may proportionally contain additional isocyanate components other than the prepolymer described. For this purpose, aromatic, araliphatic, aliphatic and cycloaliphatic di-, tri- or polyisocyanates are suitable. It is also possible to use a mixture of said di-, tri- or polyisocyanates. Examples of suitable di-, tri- or polyisocyanates include butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4- (isocyanato Methyl) octane, 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate (TMDI), isomeric bis (4,4'-isocyanatocyclohexyl) methane and any desired isomers Cyclohexylene diisocyanate, isomeric cyclohexanedimethylene diisocyanate, 1,4-phenylene diisocyanate, 2, 4-cyclohexylene diisocyanate, and mixtures thereof having a content of isocyanatomethyl-1,8-octane diisocyanate, 4- and / or 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate, triphenylmethane 4,4 ' - triisocyanate or urethane, urea, carbodiimide, acylurea , Isocyanurate, allophanate, biuret, oxadiazinetrione, derivatives of these having uretdione or iminooxyadinedione structures and mixtures thereof. Oligomers liberated from excess diisocyanate by suitable methods Preferred are those of polyisocyanates based on epoxidized and / or derivatized diisocyanates, in particular of hexamethylene diisocyanate. The oligomer isocyanurates of HDI, uretdiones and iminooxadiazines, and mixtures thereof, desirable.
또한 임의로, 이소시아네이트 성분 a)가 이소시아네이트-반응성 에틸렌계 불포화 화합물과 부분적으로 반응하는 이소시아네이트를 비례적으로 함유할 수 있다. α,β-불포화 카르복실산 유도체, 예컨대 아크릴레이트, 메타크릴레이트, 말레에이트, 푸마레이트, 말레이미드, 아크릴아미드 및 비닐 에테르, 프로페닐 에테르, 알릴 에테르, 및 디시클로펜타디에닐 단위를 함유하며 이소시아네이트에 대해 반응성인 1개 이상의 기를 갖는 화합물이 여기서 이소시아네이트-반응성 에틸렌계 불포화 화합물로서 바람직하게 사용되며; 이는 특히 바람직하게는 1개 이상의 이소시아네이트-반응성 기를 갖는 아크릴레이트 및 메타크릴레이트이다. 예를 들어, 2-히드록시에틸 (메트)아크릴레이트, 폴리에틸렌 옥시드 모노(메트)아크릴레이트, 폴리프로필렌 옥시드 모노(메트)아크릴레이트, 폴리알킬렌 옥시드 모노(메트)아크릴레이트, 폴리(ε-카프로락톤) 모노(메트)아크릴레이트, 예를 들어 톤(Tone)® M100 (다우(Dow), 미국 소재), 2-히드록시프로필 (메트)아크릴레이트, 4-히드록시부틸 (메트)아크릴레이트, 3-히드록시-2,2-디메틸프로필 (메트)아크릴레이트, 트리메틸올프로판, 글리세롤, 펜타에리트리톨, 디펜타에리트리톨, 에톡실화, 프로폭실화 또는 알콕실화 트리메틸올프로판, 글리세롤, 펜타에리트리톨, 디펜타에리트리톨과 같은 다가 알콜의 히드록시-관능성 모노-, 디- 또는 테트라(메트)아크릴레이트 또는 이들의 산업용 혼합물과 같은 화합물이 히드록시-관능성 아크릴레이트 또는 메타크릴레이트로서 적합하다. 또한, 단독의 또는 상기 언급된 단량체 화합물들과 조합된 아크릴레이트 및/또는 메타크릴레이트 기를 함유하는 이소시아네이트-반응성 올리고머 또는 중합체 불포화 화합물이 적합하다. 이소시아네이트-반응성 에틸렌계 불포화 화합물과 부분적으로 반응하는 이소시아네이트의 비율은, 이소시아네이트 성분 a)를 기준으로, 0 내지 99%, 바람직하게는 0 내지 50%, 특히 바람직하게는 0 내지 25%, 매우 특히 바람직하게는 0 내지 15%이다.Also optionally, the isocyanate component a) may proportionally contain an isocyanate which reacts in part with an isocyanate-reactive ethylenically unsaturated compound. but are not limited to, alpha, beta -unsaturated carboxylic acid derivatives such as acrylate, methacrylate, maleate, fumarate, maleimide, acrylamide and vinyl ether, propenyl ether, allyl ether, and dicyclopentadienyl units Compounds having at least one group reactive with isocyanate are preferably used herein as isocyanate-reactive ethylenically unsaturated compounds; This is particularly preferably an acrylate and a methacrylate having at least one isocyanate-reactive group. (Meth) acrylate, poly (ethylene oxide) mono (meth) acrylate, polypropylene oxide mono (meth) acrylate, polyalkylene oxide mono (meth) acrylate such as Tone 占 M100 (Dow, USA), 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) (Meth) acrylate, trimethylol propane, glycerol, pentaerythritol, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylol propane, glycerol, Hydroxy-functional mono-, di- or tetra (meth) acrylates of polyhydric alcohols such as pentaerythritol, dipentaerythritol, or industrial mixtures thereof, are known as hydroxy-functional acrylates or methacrylates As is appropriate. Also suitable are isocyanate-reactive oligomeric or polymeric unsaturated compounds containing acrylate and / or methacrylate groups alone or in combination with the above-mentioned monomeric compounds. The proportion of isocyanate partially reactive with the isocyanate-reactive ethylenically unsaturated compound is from 0 to 99%, preferably from 0 to 50%, particularly preferably from 0 to 25%, very particularly preferably from 0 to 99%, based on the isocyanate component a) Is from 0 to 15%.
임의로, 상기 언급된 이소시아네이트 성분 a)가 코팅 기술의 당업자에게 공지되어 있는 차단제와 완전히 또는 부분적으로 반응하는 이소시아네이트를 전적으로 또는 비례적으로 함유하는 것도 가능하다. 차단제의 예로는, 알콜, 락탐, 옥심, 말론산 에스테르, 알킬 아세토아세테이트, 트리아졸, 페놀, 이미다졸, 피라졸 및 아민, 예를 들어 부타논 옥심, 디이소프로필아민, 1,2,4-트리아졸, 디메틸-1,2,4-트리아졸, 이미다졸, 디에틸 말로네이트, 에틸 아세토아세테이트, 아세톤 옥심, 3,5-디메틸피라졸, ε-카프로락탐, N-tert-부틸벤질아민, 시클로펜타논 카르복시에틸 에스테르 또는 이러한 차단제들의 임의의 요망되는 혼합물이 언급될 수 있다.Optionally, it is also possible for the above-mentioned isocyanate component a) to contain wholly or partly an isocyanate which is completely or partially reacted with a blocking agent known to those skilled in the coating arts. Examples of blocking agents include alcohols, lactams, oximes, malonic acid esters, alkyl acetoacetates, triazoles, phenols, imidazoles, pyrazoles and amines such as butanone oxime, diisopropylamine, Triazole, dimethyl-1,2,4-triazole, imidazole, diethyl malonate, ethylacetoacetate, acetone oxime, 3,5-dimethylpyrazole, epsilon -caprolactam, N- Cyclopentanone carboxyethyl ester or any desired mixture of such blocking agents may be mentioned.
원칙적으로, 분자 당 평균 1.5개 이상의 이소시아네이트-반응성 기를 갖는 모든 다관능성 이소시아네이트-반응성 화합물이 성분 b)로서 사용될 수 있다.In principle, all multifunctional isocyanate-reactive compounds having an average of more than 1.5 isocyanate-reactive groups per molecule can be used as component b).
본 발명의 문맥에서 이소시아네이트-반응성 기는 바람직하게는 히드록시, 아미노 또는 티오 기이며; 히드록시 화합물이 특히 바람직하다.In the context of the present invention, the isocyanate-reactive group is preferably a hydroxy, amino or thio group; Hydroxy compounds are particularly preferred.
적합한 다관능성, 이소시아네이트-반응성 화합물은, 예를 들어, 폴리에스테르-, 폴리에테르-, 폴리카르보네이트-, 폴리(메트)아크릴레이트- 및/또는 폴리우레탄폴리올이다.Suitable polyfunctional, isocyanate-reactive compounds are, for example, polyester-, polyether-, polycarbonate-, poly (meth) acrylate- and / or polyurethane polyols.
적합한 폴리에스테르 폴리올은 예를 들어 ≥ 2의 OH 관능가를 갖는 다가 알콜과 지방족, 시클로지방족 또는 방향족 디- 또는 폴리카르복실산 또는 그의 무수물로부터 공지된 방식으로 얻을 수 있는 바와 같은 선형 폴리에스테르 디올 또는 분지형 폴리에스테르 폴리올이다.Suitable polyester polyols are, for example, linear polyester diols or alcohols, such as those obtainable in known manner from polyhydric alcohols having an OH functionality of > 2 and aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids or anhydrides thereof, Is a topographic polyester polyol.
이러한 디- 또는 폴리카르복실산 또는 무수물의 예는 숙신산, 글루타르산, 아디프산, 피멜산, 수베르산, 아젤라산, 세바스산, 노난디카르복실산, 데칸디카르복실산, 테레프탈산, 이소프탈산, o-프탈산, 테트라히드로프탈산, 헥사히드로프탈산 또는 트리멜리트산 및 산 무수물, 예컨대 o-프탈산, 트리멜리트산 또는 숙신산 무수물, 또는 이들의 임의의 요망되는 서로와의 혼합물이다.Examples of such di- or polycarboxylic acids or anhydrides include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, terephthalic acid, Isophthalic acid, o-phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid or trimellitic acid and acid anhydrides, such as o-phthalic acid, trimellitic acid or succinic anhydride, or mixtures of any of these with any desired one.
이러한 적합한 알콜의 예는 에탄디올, 디-, 트리- 또는 테트라에틸렌 글리콜, 1,2-프로판디올, 디-, 트리- 또는 테트라프로필렌 글리콜, 1,3-프로판디올, 1,4-부탄디올, 1,3-부탄디올, 2,3-부탄디올, 1,5-펜탄디올, 1,6-헥산디올, 2,2-디메틸-1,3-프로판디올, 1,4-디히드록시시클로헥산, 1,4-디메틸올시클로헥산, 1,8-옥탄디올, 1,10-데칸디올, 1,12-도데칸디올, 트리메틸올프로판, 글리세롤 또는 이들의 임의의 요망되는 서로와의 혼합물이다.Examples of such suitable alcohols are ethanediol, di-, tri- or tetraethylene glycol, 1,2-propanediol, di-, tri- or tetrapropyleneglycol, 1,3-propanediol, 1,4- , 3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-dihydroxycyclohexane, 4-dimethylolcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, trimethylolpropane, glycerol or mixtures thereof with any desired one.
폴리에스테르 폴리올은 피마자 오일과 같은 천연 원료를 기재로 할 수도 있다. 또한, 폴리에스테르 폴리올은 락톤의 단독중합체 또는 공중합체를 기재로 할 수 있으며, 이는 바람직하게는 히드록시-관능성 화합물, 예컨대 ≥ 2의 OH 관능가를 갖는 다가 알콜 (예를 들어, 상기 언급된 유형)과 락톤 또는 락톤 혼합물, 예컨대 부티로락톤, ε-카프로락톤 및/또는 메틸-ε-카프로락톤의 부가 반응에 의해 얻을 수 있다.The polyester polyol may be based on natural raw materials such as castor oil. The polyester polyol may also be based on a homopolymer or copolymer of lactone, which is preferably a hydroxy-functional compound, such as a polyhydric alcohol having an OH functionality of > = 2 ) And a lactone or lactone mixture such as butyrolactone, epsilon -caprolactone and / or methyl- epsilon -caprolactone.
이러한 폴리에스테르 폴리올은 바람직하게는 수 평균 몰 질량이 400 내지 4000 g/mol, 특히 바람직하게는 500 내지 2000 g/mol이다. 그의 OH 관능가는 바람직하게는 1.5 내지 3.5, 특히 바람직하게는 1.8 내지 3.0이다.Such a polyester polyol preferably has a number-average molar mass of 400 to 4000 g / mol, particularly preferably 500 to 2000 g / mol. Its OH functionality is preferably 1.5 to 3.5, particularly preferably 1.8 to 3.0.
적합한 폴리카르보네이트 폴리올은 그 자체로 공지된 방식으로 유기 카르보네이트 또는 포스겐을 디올 또는 디올 혼합물과 반응시킴으로써 얻을 수 있다.Suitable polycarbonate polyols can be obtained by reacting an organic carbonate or phosgene with a diol or diol mixture in a manner known per se.
적합한 유기 카르보네이트는 디메틸, 디에틸 및 디페닐 카르보네이트이다.Suitable organic carbonates are dimethyl, diethyl and diphenyl carbonate.
적합한 디올 또는 혼합물은, 폴리에스테르 부분과 관련하여 그 자체로 공지된, OH 관능가가 ≥ 2인 다가 알콜, 바람직하게는 1,4-부탄디올, 1,6-헥산디올 및/또는 3-메틸펜탄디올을 포함하거나, 또는 폴리에스테르 폴리올이 폴리카르보네이트 폴리올로 전환될 수 있다.Suitable diols or mixtures are those which are known per se in relation to the polyester part, polyhydric alcohols having an OH functionality ≥ 2, preferably 1,4-butanediol, 1,6-hexanediol and / or 3-methylpentanediol , Or the polyester polyol may be converted to a polycarbonate polyol.
이러한 폴리카르보네이트폴리올은 수 평균 몰 질량이 바람직하게는 400 내지 4000 g/mol, 특히 바람직하게는 500 내지 2000 g/mol이다. 이러한 폴리올의 OH 관능가는 바람직하게는 1.8 내지 3.2, 특히 바람직하게는 1.9 내지 3.0이다.These polycarbonate polyols preferably have a number-average molar mass of 400 to 4000 g / mol, particularly preferably 500 to 2000 g / mol. The OH functionality of such a polyol is preferably 1.8 to 3.2, and particularly preferably 1.9 to 3.0.
적합한 폴리에테르 폴리올은 임의로 OH- 또는 NH-관능성 출발물질 분자와 시클릭 에테르의 중부가물이며, 상기 중부가물은 블록 구조를 갖는다.Suitable polyether polyols are optionally the OH- or NH-functional starter molecule and the cyclic ether intermediate, and the water in the middle has a block structure.
적합한 시클릭 에테르는, 예를 들어 스티렌 옥시드, 에틸렌 옥시드, 프로필렌 옥시드, 테트라히드로푸란, 부틸렌 옥시드, 에피클로로히드린 및 이들의 임의의 요망되는 혼합물이다.Suitable cyclic ethers are, for example, styrene oxide, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin and any desired mixtures thereof.
폴리에스테르 폴리올과 관련하여 언급된 ≥ 2의 OH 관능가를 갖는 다가 알콜 및 1급 또는 2급 아민 및 아미노 알콜이 개시제로서 사용될 수 있다.Polyhydric alcohols having an OH functionality of > 2 with reference to polyester polyols and primary or secondary amines and amino alcohols can be used as initiators.
바람직한 폴리에테르 폴리올은 전적으로 프로필렌 옥시드를 기재로 하는 상기 언급된 유형의 것들, 또는 추가의 1-알킬렌 옥시드를 포함하며 상기 1-알킬렌 옥시드의 비율이 80 중량% 이하인 프로필렌 옥시드 기재의 랜덤 또는 블록 공중합체이다. 또한, 폴리(트리메틸렌 옥시드) 및 바람직한 것으로 언급된 폴리올의 혼합물이 바람직하다. 프로필렌 옥시드 단독중합체, 및 옥시에틸렌, 옥시프로필렌 및/또는 옥시부틸렌 단위를 갖는 랜덤 또는 블록 공중합체가 특히 바람직한데, 옥시프로필렌 단위의 비율은 모든 옥시에틸렌, 옥시프로필렌 및 옥시부틸렌 단위의 총량을 기준으로 20 중량% 이상, 바람직하게는 45 중량% 이상에 달한다. 여기서, 옥시프로필렌 및 옥시부틸렌은 각각의 모든 선형 및 분지형 C3 및 C4 이성질체를 포함한다.Preferred polyether polyols are those of the abovementioned type which are based entirely on propylene oxide or propylene oxide containing less than 80% by weight of said 1-alkylene oxide and further comprising 1-alkylene oxide ≪ / RTI > Also preferred are mixtures of poly (trimethylene oxide) and polyols mentioned as preferred. Particular preference is given to propylene oxide homopolymers and random or block copolymers having oxyethylene, oxypropylene and / or oxybutylene units, the proportion of oxypropylene units being such that the total amount of all oxyethylene, oxypropylene and oxybutylene units Based on the total weight of the composition, at least 20% by weight, preferably at least 45% by weight. Here, oxypropylene and oxybutylene are all linear and branched C 3 and C 4 Lt; / RTI >
이러한 폴리에테르 폴리올은 바람직하게는 250 내지 10,000 g/mol, 특히 바람직하게는 500 내지 8500 g/mol, 매우 특히 바람직하게는 600 내지 4500 g/mol의 수 평균 몰 질량을 갖는다. OH 관능가는 바람직하게는 1.5 내지 4.0, 특히 바람직하게는 1.8 내지 3.1이다.These polyether polyols preferably have a number average molar mass of 250 to 10,000 g / mol, particularly preferably 500 to 8500 g / mol, very particularly preferably 600 to 4500 g / mol. The OH functionality is preferably 1.5 to 4.0, particularly preferably 1.8 to 3.1.
또한, 다관능성 이소시아네이트-반응성 화합물로서, 저분자량을 갖고, 즉 500 g/mol 미만의 분자량을 갖고 단쇄를 갖는, 즉 2 내지 20개의 탄소 원자를 함유하는 지방족, 아르지방족 또는 시클로지방족 이관능성, 삼관능성 또는 다관능성 알콜이 또한 성분 b)의 구성성분으로서 적합하다.As the polyfunctional isocyanate-reactive compound, aliphatic, araliphatic or cycloaliphatic bifunctional compounds having a low molecular weight, that is, having a molecular weight of less than 500 g / mol and having a short chain, i.e. containing 2 to 20 carbon atoms, Functional or multifunctional alcohols are also suitable as constituents of component b).
이들은 예를 들어 에틸렌 글리콜, 디에틸렌 글리콜, 트리에틸렌 글리콜, 테트라에틸렌 글리콜, 디프로필렌 글리콜, 트리프로필렌 글리콜, 1,2-프로판디올, 1,3-프로판디올, 1,4-부탄디올, 네오펜틸 글리콜, 2-에틸-2-부틸프로판디올, 트리메틸펜탄디올, 디에틸옥탄디올의 위치 이성질체, 1,3-부틸렌 글리콜, 시클로헥산디올, 1,4-시클로헥산디메탄올, 1,6-헥산디올, 1,2- 및 1,4-시클로헥산디올, 수소화 비스페놀 A (2,2-비스(4-히드록시시클로헥실)프로판), 2,2-디메틸-3-히드록시프로피온산 (2,2-디메틸-3-히드록시프로필 에스테르)일 수 있다. 적합한 트리올의 예는 트리메틸올에탄, 트리메틸올프로판 또는 글리세롤이다. 적합한 고-관능성 알콜은 디트리메틸올프로판, 펜타에리트리톨, 디펜타에리트리톨 또는 소르비톨이다.These may be, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol , 2-ethyl-2-butylpropanediol, trimethylpentanediol, positional isomers of diethyloctanediol, 1,3-butylene glycol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6- , 1,2- and 1,4-cyclohexanediol, hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), 2,2- Dimethyl-3-hydroxypropyl ester). Examples of suitable triols are trimethylol ethane, trimethylol propane or glycerol. Suitable high-functional alcohols are ditrimethylolpropane, pentaerythritol, dipentaerythritol or sorbitol.
1종 이상의 광개시제가 성분 c)로서 사용된다. 이들은 보통 화학 방사선에 의해 활성화되고 상응하는 중합성 기의 중합을 개시할 수 있는 개시제이다. 광개시제는 그 자체로 공지된 시판되는 화합물로서, 단일분자 (유형 I) 및 이분자 (유형 II) 개시제로 구분된다. 또한, 이들 개시제는 그의 화학적 특성에 따라 자유 라디칼, 음이온성 (또는) 양이온성 (또는 혼합) 형태의 상기 언급된 중합에 사용된다.One or more photoinitiators are used as component c). These are usually initiators which are activated by actinic radiation and which are capable of initiating the polymerization of the corresponding polymerizable groups. Photoinitiators are commercially available compounds known per se and are distinguished by a single molecule (Type I) and a bispecific (Type II) initiator. These initiators are also used in the above-mentioned polymerization of free radical, anionic (or) cationic (or mixed) forms according to their chemical properties.
자유 라디칼 광중합을 위한 (유형 I) 시스템은, 예를 들어 방향족 케톤 화합물, 예를 들어 3급 아민과 조합된 벤조페논, 알킬벤조페논, 4,4'-비스(디메틸아미노)벤조페논 (미클러 케톤), 안트론 및 할로겐화 벤조페논 또는 상기 유형의 혼합물이다. (유형 II) 개시제, 예컨대 벤조인 및 그의 유도체, 벤질 케탈, 아실포스핀 옥시드, 예를 들어 2,4,6-트리메틸벤조일디페닐포스핀 옥시드, 비스아실로포스핀 옥시드, 페닐글리옥실산 에스테르, 캄포르퀴논, 알파-아미노알킬페논, 알파-, 알파-디알콕시아세토페논, 1-[4-(페닐티오)페닐]옥탄-1,2-디온 2-(O-벤조일옥심), 적합한 공개시제를 갖는 다르게 치환된 헥스아릴비스이미다졸 (HABI), 예컨대 메르캅토벤조옥사졸 및 알파-히드록시알킬페논이 추가로 적합하다. EP-A 0223587에 기재되고 암모늄 아릴보레이트 및 1종 이상의 염료의 혼합물로 이루어진 광개시제 시스템이 또한 광개시제로서 사용될 수 있다. 적합한 암모늄 아릴보레이트는, 예를 들어 테트라부틸암모늄 트리페닐헥실보레이트, 테트라부틸암모늄 트리페닐부틸보레이트, 테트라부틸암모늄 트리나프틸부틸보레이트, 테트라메틸암모늄 트리페닐벤질보레이트, 테트라(n-헥실)암모늄 (sec-부틸)트리페닐보레이트, 1-메틸-3-옥틸이미다졸륨 디펜틸디페닐보레이트, 테트라부틸암모늄 트리스-(4-tert-부틸)페닐부틸보레이트, 테트라부틸암모늄 트리스-(3-플루오로페닐)헥실보레이트 및 테트라부틸암모늄 트리스-(3-클로로-4-메틸페닐)헥실보레이트이다. 적합한 염료는, 예를 들어 뉴 메틸렌 블루, 티오닌, 베이직 옐로우, 피나시놀 클로라이드, 로다민 6G, 갈로시아닌, 에틸 바이올렛, 빅토리아(Victoria) 블루 R, 셀레스틴(Celestine) 블루, 퀴날딘 레드, 크리스탈 바이올렛, 브릴리언트 그린, 아스트라존 오렌지 G, 다로우 레드, 피로닌 Y, 베이직 레드 29, 피릴륨 I, 사프라닌 O, 시아닌 및 메틸렌 블루, 아주레 A이다 (문헌 [Cunningham et al., RadTech'98 North America UV/EB Conference Proceedings, Chicago, Apr. 19-22, 1998]).(Type I) systems for free radical photopolymerisation include, for example, aromatic ketone compounds such as benzophenone in combination with a tertiary amine, alkylbenzophenone, 4,4'-bis (dimethylamino) benzophenone Ketones), anthrons and halogenated benzophenones or mixtures of the above types. (Type II) initiators such as benzoin and its derivatives, benzyl ketal, acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacylphosphine oxide, phenylglycine (Phenylthio) phenyl] octane-1, 2-dione 2- (O-benzoyloxime) ester, camphorquinone, alpha-aminoalkylphenone, alpha-, alpha-dialkoxyacetophenone, 1- [4- , Further substituted hexaarylbisimidazoles (HABI) with suitable release agents such as mercaptobenzoxazole and alpha-hydroxyalkylphenones are further suitable. A photoinitiator system composed of a mixture of ammonium aryl borate and one or more dyes as described in EP-A 0223587 can also be used as photoinitiator. Suitable ammonium aryl borates include, for example, tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammoniumtri naphthylbutylborate, tetramethylammonium triphenylbenzylborate, tetra (n-hexyl) ammonium (4-tert-butyl) phenylbutyl borate, tetrabutylammonium tris- (3-fluorophenyl) borate, tetrabutylammonium tris ) Hexylborate and tetrabutylammonium tris- (3-chloro-4-methylphenyl) hexylborate. Suitable dyes include, for example, N-methylene blue, thionine, basic yellow, pinacinol chloride, rhodamine 6G, gallocyanine, ethyl violet, Victoria blue R, Celestine blue, , Crystal Violet, Brilliant Green, Astra Zone Orange G, Dallow Red, Pyronin Y, Basic Red 29, Pyridyl I, Saprinin O, Cyanine and Methylene Blue, and Azure A (Cunningham et al. RadTech'98 North America UV / EB Conference Proceedings, Chicago, Apr. 19-22, 1998).
음이온 중합에 사용되는 광개시제는 일반적으로 (유형 I) 시스템이고, 제1 계열의 전이 금속 착체로부터 유래한다. 여기서는, 크로뮴 염, 예를 들어 트랜스-Cr(NH3)2(NCS)4- (문헌 [Kutal et al., Macromolecules 1991, 24, 6872]) 또는 페로세닐 화합물 (문헌 [Yamaguchi et al., Macromolecules 2000, 33, 1152])이 언급되어야 한다. 음이온 중합의 추가의 가능성은 광분해성 분해에 의해 시아노아크릴레이트를 중합시킬 수 있는 염료, 예컨대 크리스탈 바이올렛, 류코니트릴 또는 말라카이트 그린 류코니트릴의 사용에 있다 (문헌 [Neckers et al., Macromolecules 2000, 33, 7761]). 그러나, 발색단이 중합체에 도입됨으로써, 생성되는 중합체가 완전히 착색된다.The photoinitiators used for anionic polymerization are generally (Type I) systems and are derived from a first series of transition metal complexes. In this example, chromium salts, such as trans -Cr (NH 3) 2 (NCS ) 4 -. ( Literature [. Kutal et al, Macromolecules 1991 , 24, 6872]) or ferrocenyl compound (lit. [Yamaguchi et al, Macromolecules 2000, 33, 1152]) should be mentioned. An additional possibility of anionic polymerization is the use of dyes capable of polymerizing cyanoacrylates by photolytic degradation, such as crystal violet, leuconitrile or malachite green leuconitrile (Neckers et al., Macromolecules 2000, 33 , 7761). However, by introducing a chromophore into the polymer, the resulting polymer is completely colored.
양이온 중합에 사용되는 광개시제는 실질적으로 하기 세 부류를 포함한다: 아릴디아조늄 염, 오늄 염 (여기서 특히: 아이오도늄, 술포늄 및 셀레노늄 염) 및 유기금속 화합물. 수소 공여체의 존재 및 부재 하에 모두 조사시, 페닐디아조늄 염은 중합을 개시하는 양이온을 생성할 수 있다. 전체 시스템의 효율은 디아조늄 화합물에 사용되는 반대이온의 특성에 의해 결정된다. 반응성이 크지는 않지만, 매우 고가인 SbF6 -, AsF6 - 또는 PF6 -이 여기서 바람직하다. 이러한 화합물들은 일반적으로 박막의 코팅에 사용하기에는 그다지 적합하지 않은데, 이는 노출 후 질소가 방출됨으로써 표면 품질이 저하되기 (핀홀) 때문이다 (문헌 [Li et al., Polymeric Materials Science and Engineering, 2001, 84, 139]). 매우 광범위하게 사용되며 또한 많은 종류의 형태로 상업적으로 입수가능한 것은 오늄 염, 특히 술포늄 및 아이오도늄 염이다. 이들 화합물의 광화학에 대해서는 오랫동안 연구되어 왔다. 여기 후, 아이오도늄 염은 초기에는 균일 분해되며, 그리하여 H 추출에 의해 안정화되며 양성자를 방출한 후 양이온성 중합을 개시하는 자유 라디칼 및 라디칼 음이온을 생성한다 (문헌 [Dektar et al., J. Org. Chem. 1990, 55, 639]; [J. Org. Chem., 1991, 56, 1838]). 이러한 메카니즘은 자유 라디칼 광중합에 대한 아이오도늄 염의 사용을 허용한다. 다시 한번, 여기서는 반대이온의 선택이 매우 중요하며, SbF6 -, AsF6 - 또는 PF6 -가 마찬가지로 바람직하다. 그렇지 않다면, 방향족의 치환의 선택은 이러한 구조 부류에서는 전적으로 자유로우며, 실질적으로 합성에 적합한 출발 빌딩 블록의 이용가능성에 의해 결정된다. 상기 술포늄 염은 노리쉬(Norrish) (II)에 따라 분해되는 화합물이다 (문헌 [Crivello et al., Macromolecules, 2000, 33, 825]). 술포늄 염의 경우 또한, 반대이온의 선택이 매우 중요한데, 그것은 실질적으로 중합체의 경화 속도에서 드러난다. 최선의 결과는 일반적으로 SbF6 염을 사용하여 얻어진다. 아이오도늄 및 술포늄 염의 자가-흡수가 < 300 nm에서 있기 때문에, 이러한 화합물들은 근 UV 또는 단파장 가시 광선에 의한 광중합에 대하여 적절하게 민감화되어야 한다. 이는 더 고도로 흡수성인 방향족물질, 예를 들어 안트라센 및 유도체 (문헌 [Gu et al., Am. Chem. Soc. Polymer Preprints, 2000, 41 (2), 1266]), 또는 페노티아진 또는 그의 유도체 (문헌 [Hua et al., Macromolecules 2001, 34, 2488-2494])의 사용에 의해 수행된다.Photoinitiators used in cationic polymerization include the following three classes: aryldiazonium salts, onium salts (in particular: iodonium, sulfonium and selenonium salts) and organometallic compounds. Upon irradiation, both in the presence and absence of a hydrogen donor, the phenyldiazonium salt can produce cations that initiate polymerization. The overall system efficiency is determined by the nature of the counterion used in the diazonium compound. SbF 6 - , AsF 6 - or PF 6 - , which are not very reactive but are very expensive, are preferred herein. These compounds are generally not very suitable for use in thin film coatings because of poor surface quality (pinholes) due to release of nitrogen after exposure (Li et al., Polymeric Materials Science and Engineering, 2001, 84 , 139). Onion salts, in particular the sulfonium and iodonium salts, are commercially available in a wide variety of forms and in many forms. The photochemistry of these compounds has long been studied. After this, the iodonium salt is initially homogeneously decomposed, thus producing free radicals and radical anions which are stabilized by H-extraction and release the protons and then initiate cationic polymerization (Dektar et al., J. Mol. Org. Chem., 1990, 55, 639; J. Org. Chem., 1991, 56, 1838). This mechanism allows the use of iodonium salts for free radical photopolymerization. Again, the choice of counterion is very important here, and SbF 6 - , AsF 6 - or PF 6 - are likewise preferred. Otherwise, the choice of aromatic substitution is entirely free in this structural class and is determined by the availability of starting building blocks that are substantially compatible with the synthesis. The sulfonium salt is a compound which decomposes according to Norrish (II) (Crivello et al., Macromolecules, 2000, 33, 825). In the case of sulfonium salts, the choice of the counterion is also very important, which is substantially revealed in the curing rate of the polymer. The best results are generally obtained using SbF 6 salts. Since the self-absorption of iodonium and sulfonium salts is < 300 nm, these compounds must be suitably sensitized for photopolymerization by near UV or short wavelength visible light. This may be achieved by adding more highly absorbing aromatics such as anthracene and derivatives (Gu et al., Am. Chem. Soc. Polymer Preprints, 2000, 41 (2), 1266) or phenothiazine or derivatives thereof (Hua et al., Macromolecules 2001, 34, 2488-2494).
이들 화합물들의 혼합물을 사용하는 것이 유리할 수도 있다. 경화에 사용되는 방사선 공급원에 따라, 광개시제의 유형 및 농도가 당업자에게 공지된 방식으로 적합화되어야 한다. 추가의 세부사항은 예를 들어 문헌 [P. K. T. Oldring (Ed.), Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol. 3, 1991, SITA Technology, London, pages 61-328]에 기재되어 있다.It may be advantageous to use mixtures of these compounds. Depending on the radiation source used for curing, the type and concentration of photoinitiator should be adapted in a manner known to those skilled in the art. Additional details can be found in, for example, < RTI ID = 0.0 > [P. K. T. Oldring (Ed.), Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol. 3, 1991, SITA Technology, London, pages 61-328.
바람직한 광개시제 c)는 테트라부틸암모늄 트리페닐헥실보레이트, 테트라부틸암모늄 트리페닐부틸보레이트, 테트라부틸암모늄 트리나프틸부틸보레이트, 테트라부틸암모늄 트리스-(4-tert-부틸)페닐부틸보레이트, 테트라부틸암모늄 트리스-(3-플루오로페닐)헥실보레이트 및 테트라부틸암모늄 트리스-(3-클로로-4-메틸페닐)헥실보레이트와 염료, 예컨대 아스트라존 오렌지 G, 메틸렌 블루, 뉴 메틸렌 블루, 아주레 A, 피릴륨 I, 사프라닌 O, 시아닌, 갈로시아닌, 브릴리언트 그린, 크리스탈 바이올렛, 에틸 바이올렛 및 티오닌의 혼합물이다.Preferred photoinitiators c) are tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium trinaphthylbutylborate, tetrabutylammonium tris- (4-tert-butyl) phenylbutylborate, tetrabutylammonium tris - (3-fluorophenyl) hexylborate and tetrabutylammonium tris- (3-chloro-4-methylphenyl) hexylborate and dyes such as AstraZone Orange G, methylene blue, , Saporin O, cyanine, gallocene, brilliant green, crystal violet, ethyl violet and thionine.
기록 단량체 성분 d)로서는, 예를 들어 US 6,780,546에 기재된 바와 같이, 광중합체 제제에 콘트라스트-부여 성분으로서 고도 굴절성 아크릴레이트를 사용하여 매우 우수한 결과를 얻을 수 있다.As the recording monomer component d), very excellent results can be obtained by using highly refractive acrylate as a contrast-imparting component in a photopolymer preparation, for example, as described in US 6,780,546.
따라서, 광중합체 제제에서, 기록 단량체가 아크릴레이트, 특히 바람직하게는 > 1.50의 굴절률을 갖는 아크릴레이트인 것이 본 발명에 따라 바람직하다. 우레탄 아크릴레이트가 매우 특히 바람직하고; 예를 들어 WO2008/125199에 기재된 바와 같이, 589 nm에서 > 1.50의 굴절률을 갖는 방향족 우레탄 아크릴레이트가 특히 바람직하다.Thus, in photopolymer formulations, it is preferred that the recording monomer is an acrylate, Is preferably an acrylate having a refractive index of > 1.50 in accordance with the present invention. Urethane acrylate is very particularly preferred; For example, as described in WO2008 / 125199, at 589 nm An aromatic urethane acrylate having a refractive index of > 1.50 is particularly preferred.
본 발명은 또한, 화학식 I의 플루오로우레탄을 사용하여 얻을 수 있는 시각적 홀로그램을 기록하기 위한 매체, 이러한 매체의 광학 소자 또는 영상으로서의 또는 영상 표현 또는 투영을 위한 용도 및 이러한 매체를 이용하는 홀로그램의 기록 방법에 관한 것이다.The present invention also relates to a medium for recording visual holograms obtainable using fluorourethanes of formula I, for use as optical elements or images of such media or for image representation or projection, and for recording holograms using such media .
본 발명에 따른 광중합체 제제는 특히 15 내지 79, 바람직하게는 30 내지 60 중량%의 매트릭스 중합체, 5 내지 50, 바람직하게는 10 내지 40 중량%의 기록 단량체, 1 내지 10, 바람직하게는 1 내지 3 중량%의 광개시제 및 5 내지 50, 바람직하게는 10 내지 40 중량%의 플루오로우레탄 및 0 내지 10 중량%의 추가의 첨가제 (여기서, 구성성분의 합계는 100 중량%임)를 함유할 수 있다.The photopolymer preparations according to the invention are particularly suitable for the preparation of photopolymer formulations comprising 15 to 79, preferably 30 to 60% by weight of a matrix polymer, 5 to 50, preferably 10 to 40% by weight of a recording monomer, 1 to 10, 3% by weight of photoinitiator and 5 to 50, preferably 10 to 40% by weight of fluorourethane and 0 to 10% by weight of further additives, wherein the sum of the constituents is 100% by weight .
본 발명의 제2 측면은, 매트릭스 중합체, 기록 단량체, 광개시제 및 가소제로서의 플루오로우레탄을 혼합하여 광중합체 제제를 얻는, 본 발명에 따른 광중합체 제제의 제조 방법에 관한 것이다.A second aspect of the present invention relates to a process for producing a photopolymer preparation according to the present invention, wherein a photopolymer preparation is obtained by mixing a matrix polymer, a recording monomer, a photoinitiator and fluorourethane as a plasticizer.
본 발명의 제3 측면은, 상기 방법에 의해 수득가능한 광중합체 제제에 관한 것이다.A third aspect of the invention relates to a photopolymer preparation obtainable by the process.
본 발명의 제4 측면은 광중합체 제제를 포함하는 시트, 필름, 층, 층 구조물 또는 성형물에 관한 것이다.A fourth aspect of the present invention relates to a sheet, film, layer, layer structure or molded article comprising a photopolymer formulation.
본 발명에 따른 광중합체 제제를 포함하는 층, 층 구조물 및 성형물은 전형적으로 Δn > 0.0120, 바람직하게는 > 0.0130, 특히 바람직하게는 > 0.0140, 매우 특히 바람직하게는 > 0.0150의, "반사 배열의 2-빔 간섭에 의한 홀로그래픽 매체의 홀로그래픽 특성 DE 및 Δn의 측정" 부분에 기재된 방법에 의해 측정되는 Δn 값을 갖는다.Layers, layered structures and moldings comprising photopolymer formulations according to the invention typically have a refractive index of 2 < / RTI > < RTI ID = 0.0 > ≪ / RTI > measured by the method described in the section " Measurement of the holographic characteristics DE and DELTA n of the holographic medium by beam interference ".
본 발명의 제5 측면은 광학 소자의 제조를 위한, 특히 홀로그래픽 소자 및 영상의 제조를 위한 광중합체 제제의 용도에 관한 것이다.A fifth aspect of the invention relates to the use of a photopolymer preparation for the manufacture of optical elements, in particular for the production of holographic elements and images.
본 발명은 또한, 기록 단량체를 전자기 방사선에 의해 공간 분해로 선택적으로 중합시키는, 본 발명에 따른 광중합체 제제를 포함하는 홀로그래픽 매체의 노출 방법에 관한 것이다.The present invention also relates to a method of exposing a holographic medium comprising a photopolymer preparation according to the invention, wherein the recording monomer is selectively polymerized by spatial resolution by electromagnetic radiation.
홀로그래픽 노출 후, 이러한 홀로그래픽 매체는, 예를 들어 광학 렌즈, 거울, 편향 거울, 필터, 확산 스크린, 회절 부재, 도광체, 도파관, 영사 스크린 및/또는 마스크의 기능을 갖는 홀로그래픽 광학 소자의 제조에 적합하다. 또한, 예를 들어 개인 초상, 보안 문서에서의 생체인식 표시, 또는 일반적인 광고용 영상물 또는 영상 구조물, 보안 라벨, 상표 보호물, 상표 브랜딩, 라벨, 디자인 요소, 장식물, 일러스트레이션, 복수-여행 티켓, 영상물 등 및 디지털 데이터를 표시할 수 있는 영상물 (특히 또한 상기한 제작물과 조합된 것)과 같은 홀로그래픽 영상물 또는 표시물을 제작할 수 있다.After the holographic exposure, such a holographic medium may be imaged onto a holographic optical element having the function of, for example, an optical lens, a mirror, a deflecting mirror, a filter, a diffusion screen, a diffractive element, a light guide, a waveguide, a projection screen and / It is suitable for manufacturing. In addition, it is also possible to use, for example, a personal portrait, a biometric identification in a security document, or a general commercial image or image structure, security label, trademark protection, trademark branding, label, design element, ornament, illustration, And a video object capable of displaying digital data (in particular, in combination with the above-described object).
선행 기술에는 특정 플루오로우레탄이 개시되어 있다. 이와 같이, US 2003/105263 A1에는 뷰렛, 이소시아누레이트, 우레트디온, 폴리우레아 함유 폴리이소시아네이트를 플루오린화 알콜과 반응시킴으로써 수득가능한 플루오로우레탄이 기재되어 있다. WO 03/023519 A에는 뷰렛-함유 폴리이소시아네이트를 플루오린화 알콜과 반응시킴으로써 수득가능한 플루오로우레탄이 개시되어 있다.The prior art discloses certain fluorourethanes. Thus, US 2003/105263 A1 describes bifluorourethanes obtainable by reacting biuret, isocyanurate, uretdione, polyurea containing polyisocyanates with fluorinated alcohols. WO 03/023519 A discloses fluorourethanes obtainable by reacting burette-containing polyisocyanates with fluorinated alcohols.
본 발명의 추가 측면은, 이미노옥사디아진디온 또는 옥사디아자디온을 함유하고, 1개 이상의 유리 이소시아네이트 기를 갖는 폴리이소시아네이트를 알콜과 반응시킴으로써 얻을 수 있는 플루오로우레탄에 관한 것이고, 여기서 폴리이소시아네이트 및/또는 알콜은 1개 이상의 플루오린 원자에 의해 치환된다.A further aspect of the present invention relates to a fluorourethane obtainable by reacting a polyisocyanate containing an iminooxyadiazide or oxadiazadione and having at least one free isocyanate group with an alcohol, wherein the polyisocyanate and / Or the alcohol is substituted by one or more fluorine atoms.
최종적으로, 본 발명은 또한 하기 화학식 III에 따른 플루오로우레탄에 관한 것이다.Finally, the present invention also relates to fluorourethanes according to formula III:
<화학식 III>(III)
상기 식에서, m은 ≥1이며, m은 ≤8이고, R4, R5, R6은 수소이고/이거나, 서로 독립적으로, 비치환되거나 또는 임의로 또한 헤테로원자에 의해 치환된 선형, 분지형, 시클릭 또는 헤테로시클릭 유기 라디칼이고, 이미노옥사디아진디온 및/또는 옥사디아자디온 구조 요소를 가지며, 동시에 라디칼 R4, R5, R6 중 적어도 2개는 1개 이상의 플루오린 원자에 의해 치환된다.Wherein m is ≥1, m is ≤8, and R 4 , R 5 , and R 6 are hydrogen and / or are independently selected from linear, branched or cyclic alkyl groups which are unsubstituted or optionally also substituted by heteroatoms, At least two of the radicals R 4 , R 5 and R 6 are optionally substituted by one or more fluorine atoms, with the proviso that at least two of the radicals R 4 , R 5 and R 6 are substituted by one or more fluorine atoms .
실시예Example ::
본 발명은 이하에서 실시예를 참조하여 보다 상세히 설명된다.The invention is described in more detail below with reference to embodiments.
달리 언급하지 않는 한, 모든 명시된 백분율은 중량 백분율 기준이다.Unless otherwise stated, all specified percentages are on a weight percent basis.
측정 방법:How to measure:
명시된 NCO 값 (이소시아네이트 함량)은 DIN EN ISO 11909에 따라 측정하였다.The stated NCO value (isocyanate content) was measured in accordance with DIN EN ISO 11909.
굴절률의 측정은, 실시예 화합물의 특성에 따라, 하기 세가지 방법 중 하나에 의해 수행하였다:The measurement of the refractive index was carried out according to the characteristics of the example compounds by one of the following three methods:
405 nm의 파장에서의 굴절률 n의 측정 (방법 A): 샘플의 파장의 함수로서의 굴절률 n을 투과 및 반사 스펙트럼으로부터 얻었다. 이를 위해, 샘플의 약 100 내지 300 nm 두께의 필름을 스핀 코팅에 의해 부틸 아세테이트 중의 희석 용액으로부터 석영 유리 기판에 도포하였다. 이러한 층 패킷의 투과 및 반사 스펙트럼은 스테아그 에타-옵틱(STEAG ETA-Optik)으로부터의 분광측정계, CD-측정 시스템 에타-알티(ETA-RT)를 사용하여 측정하였으며, 이어서 층 두께 및 n의 스펙트럼 곡선을 측정한 투과 및 반사 스펙트럼에 핏팅하였다. 이는 분광측정계의 내부 소프트웨어를 사용하여 수행하였으며, 이는 추가로 석영 유리 기판의 n 데이터를 필요로 하였는데, 이는 블랭크 측정으로 미리 측정하였다.Measurement of the refractive index n at a wavelength of 405 nm (Method A): The refractive index n as a function of the wavelength of the sample was obtained from the transmission and reflection spectra. To this end, a film about 100-300 nm thick of the sample was applied to the quartz glass substrate from the dilute solution in butyl acetate by spin coating. The transmission and reflection spectra of this layer packet were measured using a spectrometer from the STEAG ETA-Optik, a CD-measurement system ETA-RT, followed by the layer thickness and the spectrum of n Curves were fitted to the measured transmission and reflection spectra. This was done using the internal software of the spectrometer, which further required n data on the quartz glass substrate, which was measured in advance by blank measurement.
589 nm의 파장에서의 굴절률 의 측정 (방법 B): 실시예 화합물의 샘플을 아베(Abbe) 굴절계에 도입하고, 이어서,을 측정하였다.Refractive index at a wavelength of 589 nm (Method B): A sample of the example compound was introduced into an Abbe refractometer, Were measured.
반농축 용액으로부터의 589 nm의 파장에서의 굴절률 의 측정 (방법 C): 실시예 화합물의 샘플을 N-에틸피롤리돈으로 50:50 (중량%)으로 희석하고, 아베 굴절계에 도입하고, 이어서 을 측정하였다. 이로부터 분석물의 대략적 굴절률을 계산하였고; N-에틸피롤리돈의 은 1.4658이었다.Refractive index at a wavelength of 589 nm from semi-concentrated solution (Method C): A sample of the example compound was diluted to 50:50 (wt%) with N-ethyl pyrrolidone, introduced into an Abbe refractometer, Were measured. From this, the approximate refractive index of the analyte was calculated; Of N-ethylpyrrolidone Was 1.4658.
반사 배열의 2-빔 간섭에 의한 홀로그래픽 매체의 홀로그래픽 특성 DE 및 Δn의 측정Measurement of holographic characteristics DE and? N of a holographic medium by two-beam interference of a reflective array
이어서, 제조된 매체를 하기와 같이 도 1에 따른 측정 배열에 의해 그의 홀로그래픽 특성에 대하여 시험하였다:The prepared medium was then tested for its holographic properties by the measurement arrangement according to Figure 1 as follows:
He-Ne 레이저 (방출 파장 633 nm)의 빔을 조준 렌즈 (CL)와 함께 공간 필터 (SF)의 도움으로 평행한 균일 빔으로 변환시켰다. 아이리스 조리개 (I)에 의해 신호 및 기준 빔의 최종 단면을 확립하였다. 아이리스 조리개 개구의 직경은 0.4 cm였다. 편광-의존성 빔 스플리터 (PBS)는 레이저 빔을 2개의 간섭성인 동일 편광 빔으로 분할하였다. λ/2 플레이트를 통하여, 기준 빔의 전력을 0.5 mW로 조정하고, 신호 빔의 전력을 0.65 mW로 조정하였다. 전력은, 샘플을 제거하고 반도체 검출기 (D)를 사용하여 측정하였다. 기준 빔의 입사 각도 (α0)는 -21.8 °였으며, 신호 빔의 입사 각도 (β0)는 41.8 °였다. 상기 각도는 빔 방향에 대하여 수직인 샘플로부터 시작하여 측정하였다. 따라서, 도 1에 따르면, α0는 음의 부호를 가지며, β0는 양의 부호를 갖는다. 샘플 (매체)의 위치에서, 2개의 중첩하는 빔들의 간섭 장은 샘플에 입사하는 2개의 빔의 각도 이등분선에 수직인 밝고 어두운 띠들의 격자 (반사 홀로그램)를 생성하였다. 격자 주기로도 지칭되는 띠 간격 Λ는 중앙에서 약 225 nm였다 (매체의 굴절률은 약 1.504인 것으로 추정됨).The beam of the He-Ne laser (emission wavelength 633 nm) was converted into a parallel beam parallel with the collimating lens (CL) with the help of the spatial filter (SF). The final cross-section of the signal and reference beam was established by an iris aperture (I). The diameter of the iris aperture opening was 0.4 cm. A polarization-dependent beam splitter (PBS) split the laser beam into two coherent, co-polarized beams. Through the? / 2 plate, the power of the reference beam was adjusted to 0.5 mW and the power of the signal beam was adjusted to 0.65 mW. The power was measured by removing the sample and using a semiconductor detector (D). The incidence angle ( 0 ) of the reference beam was -21.8 占 and the incidence angle (? 0 ) of the signal beam was 41.8 °. The angle was measured starting from a sample perpendicular to the beam direction. Therefore, according to Fig. 1,? 0 has a negative sign and? 0 has a positive sign. At the location of the sample (medium), the interference field of the two superimposed beams produced a grid of bright and dark bands (reflective holograms) perpendicular to the angle bisector of the two beams incident on the sample. The band gap Λ, also referred to as the grating period, was about 225 nm at the center (the refractive index of the medium is estimated to be about 1.504).
도 1은 λ = 633 nm (He-Ne 레이저)에서의 홀로그래픽 매체 시험기 (HMT)의 기하학적 구조를 도시한다: M = 거울, S = 셔터, SF = 공간 필터, CL = 조준 렌즈, λ/2 = λ/2 플레이트, PBS = 편광-감응성 빔 스플리터, D = 검출기, I = 아이리스 조리개, α0 = -21.8°, β0 = 41.8° (이는 샘플의 외부 (매체의 외부)에서 측정한 간섭성 빔의 입사각임). RD = 회전반의 기준 방향.Figure 1 shows the geometry of a holographic media tester (HMT) at λ = 633 nm (He-Ne laser): M = mirror, S = shutter, SF = spatial filter, CL = = λ / 2 plate, PBS = polarization-sensitive beam splitter, D = detector, I = iris aperture, α 0 = -21.8 °, β 0 = 41.8 ° (which is the coherence The incident angle of the beam). RD = the reference direction of the ramp.
매체의 회절 효율 (DE)은 도 1에 도시된 바와 같은 홀로그래픽 실험 장치를 사용하여 측정하였다.The diffraction efficiency (DE) of the medium was measured using a holographic experimental apparatus as shown in Fig.
홀로그램을 하기 방식으로 매체에 기록하였다:The hologram was recorded on the medium in the following manner:
· 양쪽 셔터 (S)를 노출 시간 t 동안 개방하였다.Both shutters S were opened for exposure time t.
· 그 후, 셔터 (S)를 폐쇄하고, 아직까지 비중합된 기록 단량체의 확산 동안 매체에 5분의 시간을 허용하였다.Thereafter, the shutter S was closed, and the medium was allowed to stand still for 5 minutes during the diffusion of the non-polymerized recording monomer.
기록된 홀로그램을 이제 하기 방식으로 판독하였다. 신호 빔의 셔터는 폐쇄하여 유지하였다. 기준 빔의 셔터를 개방하였다. 기준 빔의 아이리스 조리개를 < 1 mm의 직경으로 폐쇄하였다. 이는 빔이 항상 완전히, 매체의 모든 회전각 (Ω)에 대하여 이전에 기록된 홀로그램 내에 있도록 보장하였다. 컴퓨터 제어 하의 회전반은 이제 0.05°의 각도 단계 폭으로 Ω최소 내지 Ω최대의 각도 범위를 포함하였다. Ω는 회전반의 기준 방향에 대하여 수직인 샘플로부터 측정하였다. 회전반의 기준 방향은 홀로그램의 기록시 기준 빔 및 신호 빔의 입사각이 동일한 크기를 갖는 경우, 즉 α0 = -31.8° 및 β0 = 31.8°인 경우 얻어진다. 이 경우, Ω기록은 0°이다. 따라서, α0 = -21.8° 및 β0 = 41.8°의 경우, Ω기록은 10°이다. 일반적으로, 홀로그램의 기록 동안 간섭장은 하기와 같다.The recorded hologram was now read in the following manner. The shutter of the signal beam was kept closed. The shutter of the reference beam was opened. The iris aperture of the reference beam was closed with a diameter of <1 mm. This ensured that the beam was always completely completely within the previously recorded hologram for all rotational angles (?) Of the medium. The rotors under computer control now contained an angular range of? Min to? Max with an angular step width of 0.05 °. ? Was measured from a sample perpendicular to the reference direction of the rotor. The reference direction of the rotating disk is obtained when the incidence angles of the reference beam and the signal beam are the same when recording the hologram, that is, when α 0 = -31.8 ° and β 0 = 31.8 °. In this case, the recording of? Is 0 °. Thus, for α 0 = -21.8 ° and β 0 = 41.8 °, the Ω recording is 10 °. In general, the interference field during recording of the hologram is as follows.
θ0은 매체의 외부에서 실험실 시스템 내에서의 반각이며, 홀로그램의 기록에 대해서는 하기와 같다.[theta] 0 is the half angle in the laboratory system outside the medium, and the recording of the hologram is as follows.
이 경우에, 따라서 θ0은 -31.8°이다. 접근되는 각각의 회전각 Ω에서, 0차로 투과된 빔의 전력을 상응하는 검출기 D에 의해 측정하고, 1차로 회절된 빔의 전력을 검출기 D에 의해 측정하였다. 회절 효율은 접근되는 각각의 각도 Ω에서 하기 비율로서 얻었다.In this case, therefore, θ 0 is -31.8 °. At each approach angle of rotation OMEGA, the power of the zero-order transmitted beam was measured by the corresponding detector D and the power of the primary diffracted beam was measured by the detector D. Diffraction efficiency was obtained at each of the approaching angles? In the following proportions.
PD는 회절 빔의 검출기에서의 전력이며, PT는 투과 빔의 검출기에서의 전력이다.P D is the power in the detector of the diffraction beam and P T is the power in the detector of the transmission beam.
상기 기재된 방법에 의해, 브래그(Bragg) 곡선 (이는 기록된 홀로그램의 회전각 Ω에 대한 함수로서의 회절 효율 η를 설명함)을 측정하고, 이를 컴퓨터에 저장하였다. 또한, 0차로 투과된 강도를 또한 회전각 Ω에 대하여 플롯팅하고, 컴퓨터에 저장하였다.By the method described above, a Bragg curve (which describes the diffraction efficiency? As a function of the rotational angle? Of the recorded hologram) was measured and stored in a computer. In addition, the zero-order transmitted intensity was also plotted against the rotation angle? And stored in a computer.
홀로그램의 최대 회절 효율 (DE = η최대), 즉 그의 피크 값은 Ω재구성의 경우에서 측정하였다. 이를 위해서, 상기 최대 값을 측정하기 위해 회절된 빔의 검출기의 위치를 변경할 필요가 있을 수도 있다.The maximum diffraction efficiency (DE =? Max ) of the hologram, i.e., its peak value, was measured in the case of? Reconstruction . To this end, it may be necessary to change the position of the detector of the diffracted beam to measure the maximum value.
이제, 비굴절률차 Δn 및 광중합체 층의 두께 d를 측정된 브래그 곡선 및 각도의 함수로서의 투과된 강도 변화로부터 결합파 이론 (문헌 [H. Kogelnik, The Bell System Technical Journal, Volume 48, November 1969, Number 9 page 2909 - page 2947] 참조)에 의해 측정하였다. 광중합의 결과로서 발생하는 두께 수축으로 인하여, 홀로그램의 띠 간격 Λ' 및 띠의 배향 (편향(slant))이 간섭 패턴의 띠 간격 Λ 및 그의 배향으로부터 벗어날 수도 있다는 것에 유의해야 한다. 따라서, 최대 회절 효율이 달성되는 각도 Λ0' 또는 회전반의 상응하는 각도 Ω재구성 또한 0 또는 상응하는 Ω기록에서 벗어날 것이다. 그 결과, 브래그 조건은 변화한다. 이러한 변화가 평가 방법에서 고려되었다. 평가 방법을 하기에 기재한다:Now, the refractive index difference n and the thickness d of the photopolymer layer can be calculated from the transmitted intensity variation as a function of the measured Bragg curves and angles (see H. Kogelnik, The Bell System Technical Journal, Volume 48, November 1969, Number 9 page 2909 - page 2947). It should be noted that due to the thickness contraction that occurs as a result of photopolymerization, the band gap? 'Of the hologram and the orientation of the band (slant) may deviate from the band gap? Of the interference pattern and its orientation. Thus, the angle? 0 'at which the maximum diffraction efficiency is achieved or the corresponding angle? Reconstruction of the turntable will also deviate from zero or the corresponding? Recording . As a result, the Bragg condition changes. These changes were considered in the evaluation method. The evaluation method is described below:
간섭 패턴이 아니라 기록된 홀로그램과 관련되는 모든 기하학적 양은 점선 양으로 표시하였다.All geometric quantities associated with recorded holograms, rather than interference patterns, are indicated by dotted lines.
코겔닉(Kogelnik)에 따르면, 반사 홀로그램의 브래그 곡선 η(Ω)에 대하여 하기 식이 성립한다.According to Kogelnik, the following equation holds for the Bragg curve? (?) Of the reflective hologram.
여기서,here,
홀로그램의 판독 ("재구성")에서는, 상기와 유사하게 기재된 바와 같이, 하기 식이 성립한다.In the reading of the hologram ("reconstruction"), the following equation holds, as described above.
브래그 조건 하에, "탈위상화" DP는 0이다. 따라서 하기와 같다.Under Bragg conditions, the "deviated state" DP is zero. Therefore,
두께 수축만이 발생한다는 가정 하에, 홀로그램 기록시 간섭장의 브래그 조건과 홀로그램 판독시 브래그 조건을 비교하여 아직 알려지지 않은 각도 β'를 측정할 수 있다. 따라서, 하기 식에 따른다.Under the assumption that only thickness shrinkage occurs, it is possible to measure an angle? 'That is yet unknown by comparing the Bragg condition of the interference field with the Bragg condition in hologram reading in hologram recording. Therefore, the following formula is satisfied.
ν는 격자 두께이며, ξ는 이조(detuning) 파라미터이고, ψ'는 기록된 굴절률 격자의 배향 (편향)이다. α' 및 β'는 홀로그램 기록시 간섭장의 각도 α0 및 β0에 상응하나, 매체에서 측정되며, 홀로그램의 격자에 적용가능하다 (두께 수축 후). n은 광중합체의 평균 굴절률이고, 1.504로 설정되었다. λ는 진공에서의 레이저 광의 파장이다.? is the grating thickness,? is the detuning parameter, and? 'is the orientation (deflection) of the recorded refractive index grating. α 'and β' correspond to the angles α 0 and β 0 of the interference field in hologram recording, but are measured in the medium and are applicable to the grating of the hologram (after thickness contraction). n is the average refractive index of the photopolymer and is set at 1.504. is the wavelength of the laser light in vacuum.
이어서, 하기와 같이 ξ=0에 대하여 최대 회절 효율 (DE = η최대)이 얻어진다.Then, the maximum diffraction efficiency (DE =? Max ) is obtained for? = 0 as follows.
도 2는 각도 이조 ΔΩ에 대하여 플롯팅된 투과 전력 PT 측정치 (우측 y축)를 실선으로서, 각도 이조 ΔΩ에 대하여 플롯팅된 회절 효율 측정치 η (좌측 y축) (검출기의 유한 크기에 의해 허용되는 경우)를 흑색 원으로서 또한 코겔닉 이론의 핏팅 (좌측 y축)을 점선으로서 도시한다.FIG. 2 shows the diffraction efficiency measurement η (left y-axis) plotted against the angular binarization ΔΩ (left y-axis) (permissible by the finite size of the detector) of the transmitted power P T measured ) Is shown as a black circle and the fitting of the Coulombic theory (left-hand y-axis) as a dotted line.
회절 효율의 측정 데이터, 이론적 브래그 곡선 및 투과 강도를, 도 2에 도시한 바와 같이, 또한 각도 이조로서 지칭되는 회전 중심각에 대하여 플롯팅하였다 ().The measurement data of the diffraction efficiency, the theoretical Bragg curves and the transmission intensities were plotted against the rotation center angle, also referred to as the angle diagonal, as shown in Figure 2 ).
DE가 알려져 있으므로, 코겔닉에 따른 이론적 브래그 곡선의 형상은 광중합체 층의 두께 d'에 의해서만 결정된다. 이후 Δn을 DE를 이용하여 주어진 두께 d'에 대해 보정하여 DE의 측정 및 이론이 항상 일치되도록 한다. 이제 이론적 브래그 곡선의 제1의 2차 최소치의 각도 위치가 투과 강도의 제1의 2차 최대치의 각도 위치와 일치하며, 추가로 이론적 브래그 곡선 및 투과 강도에 대한 반치전폭 (FWHM)이 일치할 때까지 d'를 조정한다.Since the DE is known, the shape of the theoretical Bragg curves according to cohenning is only determined by the thickness d 'of the photopolymer layer. Then Δn is corrected for a given thickness d 'using DE to ensure that the measurements and the theory of DE are always consistent. Now, if the angular position of the first secondary minimum of the theoretical Bragg curves coincides with the angular position of the first secondary maximum of the transmitted intensity, and if the FWHM for the theoretical Bragg curve and transmittance coincide To d '.
반사 홀로그램이 Ω 스캔에 의해 재구성시 동시에 회전하지만, 회절된 광에 대한 검출기가 유한의 각도 범위만을 검출할 수 있는 방향으로 인하여, 넓은 홀로그램의 브래그 곡선 (작은 d')은 Ω 스캔에서는 완전하게 검출되지 않고, 적합한 검출기 위치 설정에 따라 중앙 영역에서만 검출된다. 따라서, 브래그 곡선에 대하여 상보적인 투과 강도의 형상이 추가로 층 두께 d'를 조정하는 데에 사용된다.Although the reflection hologram rotates simultaneously during reconstruction by the Ω scan, the Bragg curve (small d ') of the wide hologram is completely detected in the Ω scan due to the direction that the detector for the diffracted light can detect only a finite angular range And is detected only in the central region according to the proper detector position setting. Therefore, the shape of the complementary transmission intensity for the Bragg curve is further used to adjust the layer thickness d '.
도 2는 결합파 이론에 따른 브래그 곡선 η (점선), 각도 이조 ΔΩ에 대한 회절 효율 측정치 (흑색 원) 및 투과 전력 (흑색의 실선)의 플롯을 도시한다.Fig. 2 shows plots of diffraction efficiency measurements (black circle) and transmission power (solid line of black) for Bragg curve 侶 (dotted line), angle doublet ΔΩ according to the coupled wave theory.
하나의 제제에 대해, DE가 홀로그램의 기록 동안 포화값에 도달하는 입사 레이저 빔의 평균 에너지 용량을 측정하기 위하여 다양한 매체 상에서의 다양한 노출 시간 t에 대하여 이러한 절차를 가능하게는 수회 반복하였다. 평균 에너지 용량 E는 하기와 같이 각도 α0 및 β0의 좌표로 나타낸 2개의 부분 빔의 전력 (Pr = 0.50 mW의 기준 빔 및 Ps = 0.63 mW의 신호 빔), 노출 시간 t 및 아이리스 조리개의 직경 (0.4 cm)으로부터 얻었다.For one formulation, this procedure was possibly repeated several times for various exposure times t on various media in order to measure the average energy capacity of the incident laser beam at which the DE reached a saturation value during recording of the hologram. The average energy capacity E is calculated as the power of the two partial beams (P r = 0.50 mW reference beam and P s = 0.63 mW signal beam) in the coordinates of the angles α 0 and β 0 , exposure time t and iris aperture (0.4 cm).
부분 빔의 전력은 사용된 각도 α0 및 β0에서 동일한 전력 밀도가 매체에서 달성되도록 조정되었다.The power of the partial beam was adjusted such that the same power density at the angles α 0 and β 0 used was achieved in the medium.
사용된 물질:Materials Used:
플루오르링크(Fluorlink) E 10/H는 솔베이 솔렉시스(Solvay Solexis)에 의해 제조되고, 750 g/mol의 평균 분자량을 갖는 플루오린화 알콜을 기재로 하는 반응성 첨가제이다.
CGI-909 (테트라부틸암모늄 트리스(3-클로로-4-메틸페닐)(헥실)보레이트, [1147315-11-4])는 시바 인크.(CIBA Inc., 스위스 바젤 소재)에 의해 제조되는 실험용 제품이다.CGI-909 (tetrabutylammonium tris (3-chloro-4-methylphenyl) (hexyl) borate, [1147315-11-4]) is an experimental product manufactured by Ciba Inc. (Basel, Switzerland) .
1,8-디이소시아네이토-4-(이소시아네이토메틸)옥탄 (TIN)을 EP749958에 기재된 바와 같이 제조하였다.Diisocyanato-4- (isocyanatomethyl) octane (TIN) was prepared as described in EP749958.
사용된 플루오린화 알콜 및 일관능성 이소시아네이트는 화학 업계로부터 얻었고, 사용된 폴리이소시아네이트 (데스모두르 H (HDI), 데스모두르 I (IPDI), 데스모두르 W, 데스모두르 LD, 데스모두르 N3400, 데스모두르 N3600, 데스모두르 N3900, 베이마이크론 OXA)는 바이엘 머티리얼사이언스 아게(Bayer MaterialScience AG, 독일 레버쿠젠 소재)의 시판품이다.The fluorinated alcohols used and monofunctional isocyanates were obtained from the chemical industry and the polyisocyanates used (all des (HDI), des all le (IPDI), des all le w, des le le LD, des le le N3400 , Death All Le N3600, Death All Le N3900, Bay Micron OXA) are commercially available from Bayer MaterialScience AG, Leverkusen, Germany.
2,4,4-트리메틸헥산 1,6-디이소시아네이트, 베스타나트(Vestanat) TMDI는 에보닉 데구사 게엠베하(Evonik Degussa GmbH, 독일 마를 소재)의 제품이다.2,4,4-
2,2,2-2,2,2- 트리플루오로에틸Trifluoroethyl (6- (6- 이소시아네이토헥실Isocyanatohexyl )) 카르바메이트의Carbamate 제조 Produce
헥사메틸렌 디이소시아네이트 (HDI) 684 g을 초기에 1 l 둥근 바닥 플라스크에 80℃에서 도입하고, 이소프탈로일 디클로라이드 0.002 g을 첨가하였다. 트리플루오로에탄올 54.4 g을 천천히 적가하고, 교반을 NCO 값이 43.2 중량%가 될 때까지 수행하였다. 혼합물을 박막 증발기 상에서 증류에 의해 분리하고, 22.7 중량%의 NCO 함량을 갖는 표제 화합물 47 g (= 이론치의 47%)을 수득하였다.684 g of hexamethylene diisocyanate (HDI) were initially introduced into a 1 l round bottom flask at 80 占 폚 and 0.002 g of isophthaloyl dichloride was added. 54.4 g of trifluoroethanol was slowly added dropwise, and stirring was carried out until the NCO value reached 43.2% by weight. The mixture was separated by distillation on a thin-film evaporator to give 47 g of the title compound (47% of theory) with an NCO content of 22.7% by weight.
2,2,3,3,4,4,5,5-2,2,3,3,4,4,5,5- 옥타플루오로펜틸Octafluoropentyl (6- (6- 이소시아네이토헥실Isocyanatohexyl )) 카르바메이트의Carbamate 제조 Produce
헥사메틸렌 디이소시아네이트 (HDI) 399 g을 초기에 1 l 둥근 바닥 플라스크에 80℃에서 도입하고, 이소프탈로일 디클로라이드 0.002 g을 첨가하였다. 2,2,3,3,4,4,5,5-옥타플루오로펜탄올 73.4 g을 천천히 적가하고, 교반을 NCO 값이 39.4 중량%가 될 때까지 수행하였다. 혼합물을 박막 증발기 상에서 증류에 의해 분리하고, 12.4 중량%의 NCO 함량을 갖는 표제 화합물 40 g (= 이론치의 40%)을 수득하였다.399 g of hexamethylene diisocyanate (HDI) were initially introduced into a 1 l round bottom flask at 80 DEG C and 0.002 g of isophthaloyl dichloride was added. 73.4 g of 2,2,3,3,4,4,5,5-octafluoropentanol was slowly added dropwise, and stirring was carried out until the NCO value reached 39.4% by weight. The mixture was separated by distillation on a thin-film evaporator, yielding 40 g (40% of theory) of the title compound with an NCO content of 12.4% by weight.
실시예Example 1: One: 비스Bis (2,2,2-(2,2,2- 트리플루오로에틸Trifluoroethyl )) 헥산Hexane -1,6--1,6- 디일Dill 비스카르바메이트Biscarbamate
데스모라피드 Z 0.07 g 및 6-디이소시아네이토헥산 (HDI) 64.4 g을 초기에 500 ml 둥근 바닥 플라스크에 도입하고, 60℃로 가열하였다. 그 후, 트리플루오로에탄올 81.5 g을 적가하고, 혼합물을 이소시아네이트 함량이 0.1% 미만으로 떨어질 때까지 추가로 60℃에서 유지하였다. 이어서, 냉각을 수행하였다. 생성물을 무색 고체로서 수득하였다.0.07 g of Desmorapride Z and 64.4 g of 6-diisocyanatohexane (HDI) were initially introduced into a 500 ml round bottom flask and heated to 60 占 폚. Then 81.5 g of trifluoroethanol was added dropwise and the mixture was further maintained at 60 C until the isocyanate content fell below 0.1%. Cooling was then performed. The product was obtained as a colorless solid.
하기 표 1에 기재된 실시예를, 명시된 조성으로 실시예 1에 기재된 방식으로 제조하였다.The examples set forth in Table 1 below were prepared in the manner described in Example 1 in the specified composition.
표 1: 실시예 2 내지 224의 제조 및 특성화Table 1: Preparation and characterization of Examples 2 to 224
실시예Example 225: 9,9,10,10,11,11,12,12,13,13,14,14,29,29,30,30,31,31,32,32, 33,33,34,34-테 225: 9,9,10,10,11,11,12,12,13,13,14,14,29,29,30,30,31,31,32,32,33,33,34,34-34. rim 트라TRA 코사플루오로-20,20,22-≪ RTI ID = 0.0 > co-fluoro-20,20,22- 트리메틸Trimethyl -6,17,26--6,17,26- 트리옥소Trioxo -7,16,27-트리옥사-5,18,25--7,16,27-trioxa-5,18,25- 트리아자펜타트리아콘탄Triazapentatriacontane -35-일 -35-day 부틸카르바메이트Butyl carbamate
2,2,3,3,4,4,5,5,6,6,7,7-도데카플루오로-1,8-옥탄디올을 초기에 250 ml 둥근 바닥 플라스크에 도입하고, 디부틸주석 디라우레이트 (데스모라피드 Z, 바이엘 머티리얼사이언스 아게 (독일 레버쿠젠 소재)) 0.05 g을 첨가하고, 60℃로 가열하였다. n-부틸 이소시아네이트 18.7 g을 여러 부분으로 나누어 첨가하고, 60℃에서 3시간 동안 교반을 수행하였다. 그 후, 2,4,4-트리메틸헥산 1,6-디이소시아네이트 (TMDI) 19.9 g을 적가하고, 혼합물을 이소시아네이트 함량이 0.1% 미만으로 떨어질 때까지 추가로 60℃에서 유지하였다. 그 후, 냉각을 수행하였고, 생성물을 무색 오일로서 수득하였고; 방법 B에 따라 측정된 굴절률은 = 1.4131이었다.2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1,8-octanediol was initially introduced into a 250 ml round bottom flask and dibutyltin 0.05 g of dilaurate (Desmorapidz Z, Bayer Material Science Ltd., Leverkusen, Germany) was added and heated to 60 占 폚. 18.7 g of n-butyl isocyanate was added in several portions and stirring was carried out at 60 DEG C for 3 hours. Thereafter, 19.9 g of 2,4,4-
실시예Example 226: 23-(8,8,9,9,10,10,11,11,12,12,13,13- 226: 23- (8,8,9,9,10,10,11,11,12,12,13,13- 도데카플루오로Dodecafluoro -5,16--5,16- 디D 옥소-6,15-Oxo-6,15- 디옥사Dioxa -4,17--4,17- 디아자헤니코스Diazahanikos -1-일)-9,9,10,10,11,11,12,12,13,13,14,14,29,29,30,30,31,31,32,32,33,33,34,34-테트라코사플루오로-6,17,26--1-yl) -9,9,10,10,11,11,12,12,13,13,14,14,29,29,30,30,31,31,32,32,33,33, 34,34-tetracosafluoro-6,17,26- 트리옥소Trioxo -7,16,27--7,16,27- 트리옥사Trioxa -5,18,25--5,18,25- 트리아자펜타트리아콘탄Triazapentatriacontane -35-일 부틸카르바메이트-35-yl butylcarbamate
2,2,3,3,4,4,5,5,6,6,7,7-도데카플루오로-1,8-옥탄디올을 초기에 100 ml 둥근 바닥 플라스크에 도입하였고, 디부틸주석 디라우레이트 (데스모라피드 Z, 바이엘 머티리얼사이언스 아게 (독일 레버쿠젠 소재)) 0.01 g을 첨가하고, 60℃로 가열하였다. n-부틸 이소시아네이트 3.63 g을 여러 부분으로 나누어 첨가하고, 60℃에서 3시간 동안 교반을 수행하였다. 그 후, 1,8-디이소시아네이토-4-(이소시아네이토메틸)옥탄 (TIN) 3.08 g을 적가하고, 혼합물을 이소시아네이트 함량이 0.1% 미만으로 떨어질 때까지 추가로 60℃에서 유지하였다. 그 후, 냉각을 수행하였고, 생성물을 무색 오일로서 수득하였고; 방법 A에 따라 측정된 굴절률은 n = 1.4200이었다.2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro-1,8-octanediol was initially introduced into a 100 ml round bottom flask and dibutyltin 0.01 g of dilaurate (Desmorapidz Z, Bayer Material Science, Leverkusen, Germany) was added and heated to 60 占 폚. 3.63 g of n-butyl isocyanate was added in several portions and stirring was carried out at 60 DEG C for 3 hours. Then 3.08 g of 1,8-diisocyanato-4- (isocyanatomethyl) octane (TIN) was added dropwise and the mixture was further maintained at 60 C until the isocyanate content fell below 0.1% . Cooling was then performed and the product was obtained as a colorless oil; The refractive index measured according to Method A was n = 1.4200.
매체의 제조Manufacture of media
광학 특성을 시험하기 위해, 하기 기재된 바와 같이 매체를 제조하고 광학적으로 측정하였다:To test the optical properties, the medium was prepared and optically measured as described below:
폴리올 성분의 제조:Preparation of polyol component:
주석 옥타노에이트 0.18 g, ε-카프로락톤 374.8 g 및 이관능성 폴리테트라히드로푸란 폴리에테르 폴리올 374.8 g (OH 1 mol 당 500 g 당량)을 초기에 1 l의 플라스크에 도입하고, 120℃로 가열하고, 고체 함량 (비휘발성 구성성분의 비율)이 99.5 중량% 이상이 될 때까지 이 온도에서 유지하였다. 그 후, 냉각을 수행하였고, 생성물을 왁스질의 고체로서 수득하였다.0.18 g of tin octanoate, 374.8 g of? -Caprolactone and 374.8 g of a difunctional polytetrahydrofuran polyether polyol (500 g equivalent per 1 mol of OH) were initially introduced into a 1 liter flask and heated to 120 ° C , And maintained at this temperature until the solids content (ratio of non-volatile constituents) was at least 99.5% by weight. Cooling was then performed and the product was obtained as a waxy solid.
우레탄 아크릴레이트 1: 포스포로티오일트리스(옥시벤젠-4,1-디일카르바모일옥시에탄-2,1-디일) 트리스아크릴레이트의 제조Urethane acrylate 1: Preparation of phosphorothioate tris (oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate
2,6-디-tert-부틸-4-메틸페놀 0.1 g, 디부틸주석 디라우레이트 (데스모라피드 Z, 바이엘 머티리얼사이언스 아게 (독일 레버쿠젠 소재)) 0.05 g 및 에틸 아세테이트 중 트리스(p-이소시아네이토페닐)티오포스페이트의 27% 농도의 용액 (데스모두르® RFE, 바이엘 머티리얼사이언스 아게 (독일 레버쿠젠 소재)의 제품) 213.07 g을 초기에 500 ml 둥근 바닥 플라스크에 도입하고, 60℃로 가열하였다. 그 후, 2-히드록시에틸 아크릴레이트 42.37 g을 적가하고, 혼합물을 이소시아네이트 함량이 0.1% 미만으로 떨어질 때까지 추가로 60℃에서 유지하였다. 그 후, 냉각을 수행하고, 진공에서 에틸 아세테이트를 완전히 제거하였다. 생성물을 반결정질 고체로서 수득하였다.0.1 g of 2,6-di-tert-butyl-4-methylphenol, 0.05 g of dibutyltin dilaurate (Desmorapid Z, Bayer Material Science, Leverkusen, Germany) cyanatophenyl) 27% solution of the thiophosphate (Rhodes both Le ® RFE, Bayer MaterialScience AG (Leverkusen, Germany material) of products) introducing 213.07 g in 500 ml round bottom flask initially and heated to 60 ℃ Respectively. Then, 42.37 g of 2-hydroxyethyl acrylate was added dropwise and the mixture was further maintained at 60 DEG C until the isocyanate content fell below 0.1%. Cooling was then performed and ethyl acetate was completely removed in vacuo. The product was obtained as a semi-crystalline solid.
우레탄 아크릴레이트 2: 2-({[3-(메틸술파닐)페닐]카르바모일}옥시)프로필 프로프-2-Urethane acrylate 2: 2 - ({[3- (methylsulfanyl) phenyl] carbamoyl} oxy) propyl] prop- 에노에이트의Enoite's 제조 Produce
2,6-디-tert-부틸-4-메틸페놀 0.05 g, 데스모라피드 Z 0.02 g, 에틸 아세테이트 50 g 중 3-(메틸티오)페닐 이소시아네이트 26.8 g을 초기에 250 ml 둥근 바닥 플라스크에 도입하고, 60℃로 가열하였다. 그 후, 2-히드록시프로필 아크릴레이트 21.1 g을 적가하고, 혼합물을 이소시아네이트 함량이 0.1% 미만으로 떨어질 때까지 추가로 60℃에서 유지하였다. 그 후, 에틸 아세테이트를 5 mbar에서 증류 제거하고, 냉각을 수행하였다. 생성물을 밝은 황색 액체로서 수득하였다.0.05 g of 2,6-di-tert-butyl-4-methylphenol, 0.02 g of Desmorapride Z and 26.8 g of 3- (methylthio) phenylisocyanate in 50 g of ethyl acetate were initially introduced into a 250 ml round bottom flask , And heated to 60 占 폚. Then, 21.1 g of 2-hydroxypropyl acrylate was added dropwise and the mixture was further maintained at 60 DEG C until the isocyanate content fell below 0.1%. Ethyl acetate was then distilled off at 5 mbar and cooling was carried out. The product was obtained as a light yellow liquid.
매체 1:Medium 1:
상기 기재한 바와 같이 제조된 폴리올 성분 3.82 g을 60℃에서 포스포로티오일트리스(옥시벤젠-4,1-디일카르바모일옥시에탄-2,1-디일) 트리스아크릴레이트 (우레탄 아크릴레이트 1) 2.50 g, 2,2,2-트리플루오로에틸 헥실카르바메이트 (실시예 4) 2.50 g, CGI 909 (시바 인크 (스위스 바젤 소재)의 실험용 제품) 0.10 g, 뉴 메틸렌 블루 0.01 g 및 N-에틸피롤리돈 0.35 g과 혼합하여 투명한 용액을 수득하였다. 그 후, 30℃로의 냉각을 수행하였고, 데스모두르® N3900 (바이엘 머티리얼사이언스 아게 (독일 레버쿠젠 소재)의 시판품, 헥산 디이소시아네이트 기재의 폴리이소시아네이트, 이미노옥사디아진디온 비율 30% 이상, NCO 함량: 23.5%) 0.71 g을 첨가하고, 혼합을 다시 수행하였다. 최종적으로, 폼레즈(Fomrez) UL 28 (우레탄화 촉매, 모멘티브 퍼포먼스 케미칼스(Momentive Performance Chemicals, 미국 코네티컷주 윌톤 소재)의 시판품) 0.006 g을 첨가하고, 혼합을 다시 짧게 수행하였다. 이어서, 수득된 액체 물질을 유리 플레이트에 붓고, 스페이서에 의해 20 ㎛의 거리를 유지하며 제2 유리 플레이트로 이를 덮었다. 이 시편을 실온에서 12시간 동안 정치시키고, 경화시켰다.3.82 g of the polyol component prepared as described above was reacted with phosphorothioyl tris (oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate (urethane acrylate 1) 2.50 g of 2,2,2-trifluoroethylhexylcarbamate (Example 4), 0.10 g of CGI 909 (experimental product of Shiba Ink, Basel, Switzerland), 0.01 g of N-methylene blue and 0.10 g of N- And mixed with 0.35 g of ethylpyrrolidone to obtain a transparent solution. Then, was carried out cooling to 30 ℃, des both Le ® N3900 (Bayer MaterialScience AG (commercial products of Leverkusen, Germany material), a polyisocyanate of hexane diisocyanate base, already nook Saadi-triazine-dione ratio more than 30%, NCO content: 23.5%) were added, and mixing was carried out again. Finally, 0.006 g of Fomrez UL 28 (a urethanization catalyst commercially available from Momentive Performance Chemicals, Wilton, Conn.) Was added and mixing was again briefly carried out. The resulting liquid material was then poured into a glass plate, which was kept at a distance of 20 [mu] m by a spacer and covered with a second glass plate. The specimens were allowed to stand at room temperature for 12 hours and cured.
매체 2 내지 13을 표 1에 나타낸 실시예로부터 유사한 방식으로 제조하였다. 각 경우에, 표 2에는 광중합체 제제 중에 어떠한 실시예 화합물이 얼마의 함량으로 존재하였는지가 명시되어 있다. 제조된 광중합체 제제에 대해 측정된 Δn 값을 또한 표 2에 요약하였다.Media 2 to 13 were prepared in a similar manner from the examples shown in Table 1. In each case, Table 2 specifies how much of the example compound was present in the photopolymer formulation. The measured [Delta] n values for the prepared photopolymer formulation are also summarized in Table 2. [
매체 14:Medium 14:
상기 기재한 바와 같이 제조된 폴리올 성분 3.40 g을 60℃에서 포스포로티오일트리스(옥시벤젠-4,1-디일카르바모일옥시에탄-2,1-디일) 트리스아크릴레이트 (우레탄 아크릴레이트 1) 2.00 g, 2-({[3-(메틸술파닐)페닐]카르바모일}옥시)프로필 프로프-2-에노에이트 (우레탄 아크릴레이트 2) 2.00 g, 2,2,2-트리플루오로에틸 헥실카르바메이트 (실시예 4) 1.50 g, CGI 909 (시바 인크 (스위스 바젤 소재)의 실험용 제품) 0.10 g, 뉴 메틸렌 블루 0.01 g 및 N-에틸피롤리돈 0.35 g과 혼합하여 투명한 용액을 수득하였다. 그 후, 30℃로의 냉각을 수행하였고, N3900 (바이엘 머티리얼사이언스 아게 (독일 레버쿠젠 소재)의 시판품, 헥산 디이소시아네이트 기재의 폴리이소시아네이트, 이미노옥사디아진디온 비율 30% 이상, NCO 함량: 23.5%) 0.64 g을 첨가하고, 혼합을 다시 수행하였다. 최종적으로, 폼레즈 UL 28 (우레탄화 촉매, 모멘티브 퍼포먼스 케미칼스 (미국 코네티컷주 윌톤 소재)의 시판품) 0.006 g을 첨가하고, 혼합을 다시 짧게 수행하였다. 이어서, 수득된 액체 물질을 유리 플레이트에 붓고, 스페이서에 의해 20 ㎛의 거리를 유지하며 제2 유리 플레이트로 이를 덮었다. 이 시편을 실온에서 12시간 동안 정치시키고, 경화시켰다.3.40 g of the polyol component prepared as described above was reacted with phosphorothioyl tris (oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate (urethane acrylate 1) 2.00 g of 2-ethylhexyl acrylate, 2.00 g of 2 - ({[3- (methylsulfanyl) phenyl] carbamoyl} oxy) propylprop-2-enoate (urethane acrylate 2) 1.50 g of hexylcarbamate (Example 4), 0.10 g of CGI 909 (experimental product of Shiba Ink, Basel, Switzerland), 0.01 g of N-methylene blue and 0.35 g of N-ethylpyrrolidone to obtain a clear solution Respectively. Thereafter, cooling to 30 ° C was carried out, and N3900 (commercial product of Bayer Material Science Ltd., Leverkusen, Germany), polyisocyanate based on hexane diisocyanate, iminooxadiazine ratio of 30% or more, NCO content: 23.5%) 0.64 g was added, and mixing was carried out again. Finally, 0.006 g of Pomlet's UL 28 (urethane catalyst, marketed by Momentive Performance Chemicals, Wilton, Conn.) Was added and mixing was again briefly performed. The resulting liquid material was then poured into a glass plate, which was kept at a distance of 20 [mu] m by a spacer and covered with a second glass plate. The specimens were allowed to stand at room temperature for 12 hours and cured.
매체 14 내지 70을 표 1에 나타낸 실시예로부터 유사한 방식으로 제조하였다. 각 경우에, 표 3에는 광중합체 제제 중에 어떠한 실시예 화합물이 얼마의 함량으로 존재하였는지가 명시되어 있다. 제조된 광중합체 제제에 대해 측정된 Δn 값을 또한 표 3에 요약하였다.Media 14 to 70 were prepared in a similar manner from the examples shown in Table 1. In each case, Table 3 specifies how much of the exemplary compound was present in the photopolymer formulation. The measured Δn values for the prepared photopolymer preparations are also summarized in Table 3.
비교용 매체 I:Comparative medium I:
상기 기재한 바와 같이 제조된 폴리올 성분 8.89 g을 60℃에서 포스포로티오일트리스(옥시벤젠-4,1-디일카르바모일옥시에탄-2,1-디일) 트리스아크릴레이트 (우레탄 아크릴레이트 1) 3.75 g, CGI 909 (시바 인크 (스위스 바젤 소재)의 실험용 제품) 0.15 g, 뉴 메틸렌 블루 0.015 g 및 N-에틸피롤리돈 0.53 g과 혼합하여 투명한 용액을 수득하였다. 그 후, 30℃로의 냉각을 수행하였고, 데스모두르® N3900 (바이엘 머티리얼사이언스 아게 (독일 레버쿠젠 소재)의 시판품, 헥산 디이소시아네이트 기재의 폴리이소시아네이트, 이미노옥사디아진디온 비율 30% 이상, NCO 함량: 23.5%) 1.647 g을 첨가하고, 혼합을 다시 수행하였다. 최종적으로, 폼레즈 UL 28 (우레탄화 촉매, 모멘티브 퍼포먼스 케미칼스 (미국 코네티컷주 윌톤 소재)의 시판품) 0.009 g을 첨가하고, 혼합을 다시 짧게 수행하였다. 이어서, 수득된 액체 물질을 유리 플레이트에 붓고, 스페이서에 의해 20 ㎛의 거리를 유지하며 제2 유리 플레이트로 이를 덮었다. 이 시편을 실온에서 12시간 동안 정치시키고, 경화시켰다.8.89 g of the polyol component prepared as described above was reacted with phosphorothioyl tris (oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate (urethane acrylate 1) 3.75 g, 0.15 g of CGI 909 (experimental product of Shiba Ink, Basel, Switzerland), 0.015 g of N-methylene blue and 0.53 g of N-ethylpyrrolidone to give a clear solution. Then, was carried out cooling to 30 ℃, des both Le ® N3900 (Bayer MaterialScience AG (commercial products of Leverkusen, Germany material), a polyisocyanate of hexane diisocyanate base, already nook Saadi-triazine-dione ratio more than 30%, NCO content: 23.5%), and the mixing was carried out again. Finally, 0.009 g of Pomlet's UL 28 (urethane catalyst, marketed by Momentive Performance Chemicals, Wilton, Conn.) Was added and mixing was again briefly performed. The resulting liquid material was then poured into a glass plate, which was kept at a distance of 20 [mu] m by a spacer and covered with a second glass plate. The specimens were allowed to stand at room temperature for 12 hours and cured.
비교용 매체 Comparison medium IIII ::
상기 기재한 바와 같이 제조된 폴리올 성분 3.82 g을 60℃에서 포스포로티오일트리스(옥시벤젠-4,1-디일카르바모일옥시에탄-2,1-디일) 트리스아크릴레이트 (우레탄 아크릴레이트 1) 2.50 g, 프로필렌 카르보네이트 (비교 실시예 II) 2.50 g, CGI 909 (시바 인크 (스위스 바젤 소재)의 실험용 제품) 0.10 g, 뉴 메틸렌 블루 0.010 g 및 N-에틸피롤리돈 0.35 g과 혼합하여 투명한 용액을 수득하였다. 그 후, 30℃로의 냉각을 수행하였고, 데스모두르® N3900 (바이엘 머티리얼사이언스 아게 (독일 레버쿠젠 소재)의 시판품, 헥산 디이소시아네이트 기재의 폴리이소시아네이트, 이미노옥사디아진디온 비율 30% 이상, NCO 함량: 23.5%) 0.702 g을 첨가하고, 혼합을 다시 수행하였다. 최종적으로, 폼레즈 UL 28 (우레탄화 촉매, 모멘티브 퍼포먼스 케미칼스 (미국 코네티컷주 윌톤 소재)의 시판품) 0.022 g을 첨가하고, 혼합을 다시 짧게 수행하였다. 이어서, 수득된 액체 물질을 유리 플레이트에 붓고, 스페이서에 의해 20 ㎛의 거리를 유지하며 제2 유리 플레이트로 이를 덮었다. 이 시편을 실온에서 12시간 동안 정치시키고, 경화시켰다.3.82 g of the polyol component prepared as described above was reacted with phosphorothioyl tris (oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate (urethane acrylate 1) 2.50 g of propylene carbonate (Comparative Example II), 0.10 g of CGI 909 (experimental product of Cibaine, Basel, Switzerland), 0.010 g of N-methylene blue and 0.35 g of N-ethylpyrrolidone A clear solution was obtained. Then, was carried out cooling to 30 ℃, des both Le ® N3900 (Bayer MaterialScience AG (commercial products of Leverkusen, Germany material), a polyisocyanate of hexane diisocyanate base, already nook Saadi-triazine-dione ratio more than 30%, NCO content: 23.5%) were added, and the mixing was carried out again. Finally, 0.022 g of Pomlet's UL 28 (urethanization catalyst, marketed by Momentive Performance Chemicals, Wilton, Conn.) Was added and mixing was again briefly performed. The resulting liquid material was then poured into a glass plate, which was kept at a distance of 20 [mu] m by a spacer and covered with a second glass plate. The specimens were allowed to stand at room temperature for 12 hours and cured.
비교용 매체 III 내지 V를 표 2에 나타낸 비교 실시예로부터 유사한 방식으로 제조하였다.Comparative media III to V were prepared in a similar manner from the comparative examples shown in Table 2.
비교용 매체 Comparison medium VIVI ::
상기 기재한 바와 같이 제조된 폴리올 성분 4.66 g을 60℃에서 포스포로티오일트리스(옥시벤젠-4,1-디일카르바모일옥시에탄-2,1-디일) 트리스아크릴레이트 (우레탄 아크릴레이트 1) 2.00 g, 2-({[3-(메틸술파닐)페닐]카르바모일}옥시)프로필 프로프-2-에노에이트 (우레탄 아크릴레이트 2) 2.00 g, CGI 909 (시바 인크 (스위스 바젤 소재)의 실험용 제품) 0.10 g, 뉴 메틸렌 블루 0.010 g 및 N-에틸피롤리돈 0.35 g과 혼합하여 투명한 용액을 수득하였다. 그 후, 30℃로의 냉각을 수행하였고, 데스모두르® N3900 (바이엘 머티리얼사이언스 아게 (독일 레버쿠젠 소재)의 시판품, 헥산 디이소시아네이트 기재의 폴리이소시아네이트, 이미노옥사디아진디온 비율 30% 이상, NCO 함량: 23.5%) 0.87 g을 첨가하고, 혼합을 다시 수행하였다. 최종적으로, 폼레즈 UL 28 (우레탄화 촉매, 모멘티브 퍼포먼스 케미칼스 (미국 코네티컷주 윌톤 소재)의 시판품) 0.006 g을 첨가하고, 혼합을 다시 짧게 수행하였다. 이어서, 수득된 액체 물질을 유리 플레이트에 붓고, 스페이서에 의해 20 ㎛의 거리를 유지하며 제2 유리 플레이트로 이를 덮었다. 이 시편을 실온에서 12시간 동안 정치시키고, 경화시켰다.4.66 g of the polyol component prepared as described above was reacted with phosphorothioyl tris (oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate (urethane acrylate 1) 2.00 g of 2-ethylhexyl acrylate 2, 2.00 g of 2 - ({[3- (methylsulfanyl) phenyl] carbamoyl} oxy) propylprop-2-enoate (urethane acrylate 2), CGI 909 , 0.010 g of N-methylene blue and 0.35 g of N-ethylpyrrolidone to give a clear solution. Then, was carried out cooling to 30 ℃, des both Le ® N3900 (Bayer MaterialScience AG (commercial products of Leverkusen, Germany material), a polyisocyanate of hexane diisocyanate base, already nook Saadi-triazine-dione ratio more than 30%, NCO content: 23.5%) were added, and the mixing was carried out again. Finally, 0.006 g of Pomlet's UL 28 (urethane catalyst, marketed by Momentive Performance Chemicals, Wilton, Conn.) Was added and mixing was again briefly performed. The resulting liquid material was then poured into a glass plate, which was kept at a distance of 20 [mu] m by a spacer and covered with a second glass plate. The specimens were allowed to stand at room temperature for 12 hours and cured.
표 2: 25%의 우레탄 아크릴레이트 1 및 25%의 첨가제 (플루오린화 우레탄)를 함유하는 제제에서 선택된 실시예의 홀로그래픽 평가.Table 2: Holographic evaluation of an embodiment selected from formulations containing 25
Δn에 대해 기재된 값은 4 내지 32 mJ/㎠의 용량에서 달성되었다.Values described for [Delta] n have been achieved at a dose of 4 to 32 mJ / cm < 2 >.
홀로그래픽 매체의 홀로그래픽 특성 Δn에 대해 나타난 값은, 비교용 매체에 사용된 시판용 첨가제가 홀로그래픽 매체에 사용하기에 덜 적합한 반면, 본 발명에 따른 우레탄은 보다 높은 Δn 값으로 인해 홀로그래픽 매체의 제조를 위해 매체 1 내지 13에서 매우 적합하다는 것을 보여준다.The value shown for the holographic characteristic? N of the holographic medium is less favorable for use in holographic media, whereas the commercially available additives used in the comparative medium are less suitable for use in holographic media, whereas the urethanes according to the invention have a higher? Lt; RTI ID = 0.0 >
표 3: 20 중량%의 우레탄 아크릴레이트 1, 20 중량%의 우레탄 아크릴레이트 2 및 15 중량%의 첨가제 (플루오린화 우레탄)를 함유하는 제제에서 선택된 실시예의 홀로그래픽 평가.Table 3: Holographic evaluation of an embodiment selected from the formulations containing 20% by weight of
Δn에 대해 기재된 값은 4 내지 32 mJ/㎠의 용량에서 달성되었다.Values described for [Delta] n have been achieved at a dose of 4 to 32 mJ / cm < 2 >.
홀로그래픽 매체의 홀로그래픽 특성 Δn에 대해 나타난 값은, 본 발명에 따른 플루오린화 우레탄이 높은 Δn 값으로 인해 홀로그래픽 매체의 제조를 위해 매체 14 내지 70에서 매우 적합하다는 것을 보여준다.The values shown for the holographic characteristic? N of the holographic medium show that the fluorinated urethanes according to the invention are very suitable for media 14 to 70 for the production of holographic media due to their high? N values.
Claims (15)
<화학식 I>
The photopolymer formulation according to claim 1, wherein the fluorourethane has at least one structural element of the formula (I) and is substituted by at least one fluorine atom.
(I)
<화학식 II>
상기 식에서, n은 ≥ 1이며, n은 ≤ 8이고, R1, R2, R3은 수소이고/거나, 서로 독립적으로 비치환되거나 또는 임의로 또한 헤테로원자에 의해 치환된 선형, 분지형, 시클릭 또는 헤테로시클릭 유기 라디칼이며, 라디칼 R1, R2, R3 중 적어도 1개는 1개 이상의 플루오린 원자에 의해 치환된다.3. The photopolymer formulation according to claim 1 or 2, characterized in that the fluorourethanes have the formula (II)
≪
Wherein n is ≥ 1, n is ≤ 8, R 1 , R 2 , and R 3 are hydrogen and / or are independently selected from linear, branched, or cyclic Or a heterocyclic organic radical, and at least one of the radicals R 1 , R 2 , R 3 is substituted by one or more fluorine atoms.
R1이 1 내지 20개의 CF2 기, 1개 이상의 CF3 기, 또는 둘 다를 포함,
R2가 C1-C20 알킬 라디칼, 또는 수소를 포함, 및
R3이 C1-C20 알킬 라디칼, 또는 수소를 포함.A photopolymer formulation according to claim 3, characterized in that it satisfies at least one of the following substituent definitions:
R 1 comprises from 1 to 20 CF 2 groups, one or more CF 3 groups, or both,
R 2 is a C 1 -C 20 alkyl radical, or hydrogen, and
R 3 comprises a C 1 -C 20 alkyl radical, or hydrogen.
<화학식 III>
상기 식에서, m은 ≥1이며, m은 ≤8이고, R4, R5, R6은 수소이고/이거나, 서로 독립적으로, 비치환되거나 또는 임의로 또한 헤테로원자에 의해 치환된 선형, 분지형, 시클릭 또는 헤테로시클릭 유기 라디칼이고, 이미노옥사디아진디온 및/또는 옥사디아자디온 구조 요소를 가지며, 동시에 라디칼 R4, R5, R6 중 적어도 2개는 1개 이상의 플루오린 원자에 의해 치환된다.A fluorourethane according to formula (III):
(III)
Wherein m is ≥1, m is ≤8, and R 4 , R 5 , and R 6 are hydrogen and / or are independently selected from linear, branched or cyclic alkyl groups which are unsubstituted or optionally also substituted by heteroatoms, At least two of the radicals R 4 , R 5 and R 6 are optionally substituted by one or more fluorine atoms, with the proviso that at least two of the radicals R 4 , R 5 and R 6 are substituted by one or more fluorine atoms .
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JP2017071790A (en) | 2017-04-13 |
JP2016145352A (en) | 2016-08-12 |
PL2497082T3 (en) | 2013-12-31 |
CN102667934B (en) | 2015-09-09 |
JP2013510203A (en) | 2013-03-21 |
US8999608B2 (en) | 2015-04-07 |
BR112012010471B1 (en) | 2020-10-20 |
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